JPH0465385A - Metal thin film formation method - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a metal thin film forming method, and particularly to a thin film forming method A that can be preferably applied to wiring of semiconductor integrated circuit devices and the like.

[Conventional technology] Conventionally, electronic devices and integrated circuits (LSI) using semiconductors have been developed.
), electrodes and wiring are mainly made of aluminum (Al
) or Al-5i, etc. have been used. L is inexpensive and has high electrical conductivity (and because a dense oxide film is formed on the surface, the inside is chemically protected and stabilized, and it has good adhesion with Si). , has many advantages.

Incidentally, with the increase in the degree of integration of ultra-LSIs and the like, miniaturization of wiring and multilayer wiring have become especially necessary in recent years. Aj
As a method for depositing two films, a deposition method with excellent step coverage is required to prevent wiring breaks at step portions. In addition, a method is required that can provide good step coverage even into peer holes such as minute contact holes and through holes, or can selectively deposit onto the peer holes. Furthermore, it is necessary to have highly reliable wiring with excellent resistance to electromigration and stress migration.

In conventional LSIs, a taper is provided at the step portion to prevent deterioration of step coverage at the step portion, but as miniaturization progresses, it is no longer possible to provide a taper at the step portion, resulting in a vertical step. Since the sputtering method is based on the linear movement of particles in a vacuum, the film thickness at vertical step areas is inevitably thinner than at areas other than the step area, making it difficult to maintain good step coverage. Moreover, even at the pier hole location, the pier hole cannot be completely filled, and a hole or the like is generated within the pier hole, making it impossible to form a good contact.

A chemical vapor deposition method C, hereinafter abbreviated as CVD method, in which a gas containing 8ρ is transported to a space where a substrate is placed, and a desired deposited film is formed using adsorption and reaction of the raw material gas on the substrate surface. ) can deposit Al2, Al-SAl. The CVD method utilizes the adsorption and reaction of the raw material gas on the surface of the substrate, so it is characterized by excellent step coverage at stepped portions.

Also, selective deposition is possible depending on the type of substrate surface.

Al CVD generally uses trimethylaluminum ((CH3)!Al2 or later TMA), triisobutylaluminum ((ic, H9)mAl, hereinafter TIBA), dimethylaluminum hydride ((
Organic metal raw materials such as CH3)2HAj2 (hereinafter referred to as DMAH) are used. As is well known, AlCV
The Al film deposited by the D method has better step coverage than the sputtering method.

In addition, in Al2 CVD, SiO2 formed Si
It is also possible to selectively deposit only the exposed portions of Si on the substrate surface.

CVD method using DMAI (and hydrogen) (Tsubouchi et al.: “Nikkei Microdevice J June 1990 IE1 issue, p.96
~p102), it is possible to selectively grow Al or Al2-Si only on a conductive substrate such as Si or metal, and the l selectively deposited on the Si substrate is a single crystal.

Since the Al region is selectively grown on Si and is single crystal, there is no erosion or spikes at the Si interface during heat treatment (no deterioration of contact resistance.
．． After being selectively deposited in the pier hole, it can be deposited on the entire surface of the substrate, and it is possible to completely flatten the pier hole and deposit Af2 or Al-3Al. Therefore, it is possible to form good interconnects that do not cause disconnections at step portions, contact portions, and peer hole portions in ultra-LSIs where miniaturization is progressing.

Electromigration (hereinafter abbreviated as EM) is a phenomenon in which wiring breaks when a current continues to flow through the wiring. It is said that wire breaks occur at grain boundaries of Aff wires. In addition, stress migration (hereinafter referred to as SM)
) is a phenomenon in which stress is generated in the If wiring due to an insulating film such as SiO or SiN formed on the Al wiring, causing disconnection of the Al wiring. Generally Al2
Alternatively, Al-5i is crystallographically polycrystalline. A polycrystal is a state in which grains that are single crystals are gathered microscopically, and each single crystal region is called a crystal grain, and the boundary between crystal grains is called a grain boundary. Generally, the size of crystal grains in a VLSI is on the order of μm. EM and SM are Al or Al1. -It is a major cause of reducing the reliability of 3i wiring, and it is extremely important to improve EM and 3M resistance.
This is an essential issue for improving the reliability of SI wiring metals.

To improve EM and 3M resistance, Al2 or Al-
Methods such as adding a small amount of Cu or TAl to Si, and methods using metals other than Aj2 such as W, Mo, Cu, etc. are being considered, but there are problems with adhesion with SiO2, bonding properties, ease of microfabrication, etc. If all conditions are to be met, there is no choice other than Al or β-3i.

International Elect (IEDM) held in December 1989 by the Institute of Electrical and Electronics Engineers (IEEE)
ron Devices Meeting) Digest p. 677-p. 681 reports that if Al is a single crystal, both EM and 3M resistance will be significantly improved.

In other words, even if it is Al2 or Al-3i, it is not polycrystalline as in the past (if wiring can be formed with single crystal,
Satisfying adhesion, bonding properties, and ease of microfabrication,
Moreover, highly reliable wiring that does not cause disconnection due to EM or SM can be realized. However, in VLSI, single-crystal Al or Al-Si wiring, as described below,
It had not been realized.

There are reports that single-crystal i thin films have been realized, but all of these were realized on Si single-crystal substrates.

The report that EM and 3M resistance is improved by using single crystal Al (1989 I EDM Digest, supra) is also a result of measurements using an Al film formed by CVD on a Si substrate. l or Af2- in VLSI
Most of the 3i wiring is formed on an insulator such as 5iOz. On insulators such as SiO□, sputtering method,
In both the CVD method and the ICB (ion cluster beam) method, the material is polycrystalline, consisting of crystal grains with a grain size on the order of μm.

According to Tsubouchi et al. (cited above), it is possible to first selectively deposit single crystal AI (first l) only in the peer hole, and then deposit the second Ap on the entire surface of the wafer and the entire surface of the substrate. However, the first i is a single crystal, but the second l is still μm
It is a polycrystalline structure consisting of crystal grains of the order of magnitude.

The present invention has been made in view of the above situation, and is
This is based on the discovery that even if an Ap film is on an insulator such as iO□, if β exists in the lower layer to a single crystal, even Ap2 on an insulator can be made into a single crystal by heat treatment. .

[Problems to be Solved by the Invention] As described above, in recent years, in the field of semiconductor technology where higher integration and higher speed due to further miniaturization have been desired, it has been found that highly integrated and high performance semiconductor devices have been developed. There was a lot of room for improvement in order to improve reliability.

The present invention was made in view of the above-mentioned technical problems, and provides a method for monocrystalizing a non-single-crystal metal thin film, particularly an Ap or Aff-5j wiring layer, thereby improving the migration resistance characteristics of the wiring. The purpose is to

[Means for Solving the Problems 1] In order to achieve such an object, the present invention provides a non-single-crystal metal film made of Ap or a /1 alloy mainly composed of It is characterized by comprising a step of forming the non-single crystal metal film in contact with a single-crystal metal made of an Al-gold alloy containing ρ as a main component, and a step of heating the non-single-crystal metal film to make at least a portion of it into a single crystal.

Furthermore, the present invention includes a step of forming an insulating film on a main surface of a semiconductor substrate, a step of providing an opening in the insulating film to expose the surface of the semiconductor, and a step of forming an insulating film containing Ap or Ap as a main component in the opening. depositing a single crystal made of a first metal made of an Al-gold alloy; and depositing a second single crystal made of Ap or an alloy containing Ap as a main component on the single crystal made of the first metal and on the insulating film. forming a thin film of the second metal; and heating the thin film of the second metal using a single crystal of the first metal as a seed crystal to make at least a part of it into a single crystal. shall be.

[Function] According to the present invention, by heating the non-single-crystal metal thin film in contact with the single-crystal metal, the non-single-crystal metal thin film can be made into a single crystal using the single-crystal metal as a seed crystal. Migration resistance can be improved by using such a single crystal thin film as a wiring layer of a semiconductor device.

[Example] In a preferred embodiment of the present invention, a non-single crystal A [is made into a single crystal by applying heat treatment to an l film in which at least a portion of a single crystal core and a non-single crystal 1 are in contact with each other. It is something to do.

At this time, the method of forming single-crystal Al that will serve as a seed (seed crystal) is dimethylaluminum nohydride (
AQ (CH3) 2H), monomethylaluminum hydride (Ap(CH3>H2)), and triisobutylene aluminum (Ap2.(iC,H9)3) were used as raw material gases to deposit on single-crystal Si using the CVD method. A preferred method is to deposit l to form single crystal Al.

On the other hand, methods for forming non-single crystal Al include a method in which Ap is deposited on a surface made of a material other than the single crystal 1 by a CVD method using the above gas to form polycrystalline Al;
There are a method of forming polycrystalline Aj2 by sputtering, a method of forming polycrystalline Aj2 using trimethylaluminum (8ρ(CH3)3) and diethylaluminum chloride (Ap(c2Hs)2cp), and the like.

Single crystal A [seed may be provided so that at least a portion of 4 is in contact with the non-single crystal to be made into a single crystal. For example, the seeds and the insulating film may be formed in a lattice pattern, the seeds may be deposited in a peer hole pattern formed in the insulating film, or the seeds and the insulating film may form a line-and-space pattern. Good too.

Another preferred embodiment of the present invention is to use a single crystal formed in an opening (pier hole) formed in an insulating film as a seed (seed crystal) to form a non-single crystal Al in other parts.
is heated to form a single crystal. In particular, after L is selectively deposited in the peer hole to form β in the single crystal, Aj2 is non-selectively deposited also on the insulating film. Then, it is preferable to perform heat treatment to single-crystallize l on the insulating film. If such a method is used, a flat Al film can be formed on the peer hole without forming a concave portion.

A method for forming single crystal Al as a seed is CV using an alkyl aluminum hydride and hydrogen.
Method D (Al-CVD method) is preferred. By using this CVD method, Al can be selectively deposited on an electron-donating surface such as single crystal Si.

Alkylaluminium hydride is dimethylaluminum hydride (i (C1(3)2H)) or monomethylaluminum hydride (,l CH3H2).The method for forming non-single crystal Al before single crystallization is the usual sputtering method. method and CVD method.

When using the CVD method, raw material gases include trimethylaluminum (Al(CH,M), triisobutylaluminum Al (xc4He)3, and diethylaluminum chloride Al(C2H5)2C°C. If such a method is used, semiconductor devices can be This makes it possible to form suitable wiring.

This embodiment will be described in detail below with reference to the drawings.

FIG. 1 is a schematic cross-sectional view for explaining an example in which the single crystallization method according to the present invention is utilized for forming wiring.

In FIG. 1(a), 1 is a base made of single crystal Si or the like;
2 is an insulating film made of silicon oxide or the like, 3 is a single crystal Al serving as a seed, and 4 is single crystallized by a single crystallization method described later. It is l.

First, an insulating film 2 is formed on a base 1.

Then, a pier hole is formed by reactive ion etching or the like to partially expose the surface of the substrate 1.

Here, the insulating films include NSG, PSG, BSG-,
The film may be a silicon oxide film such as BPSG, a silicon nitride film, a silicon oxynitride film, or the like. These films can be formed by well-known thermal oxidation methods, CVD methods, sputtering methods, and the like.

Next, single crystal Al (first i) 3 is formed in the peer hole. In this case, if the above-mentioned Aj2CVD method is used, single crystal A[ can be formed in the peer hole with good selectivity. At this time, the substrate surface temperature is above the decomposition temperature of alkyl aluminum hydride and below 450°C.
More preferably 260°C or more and 440°C or less, optimally 2
The temperature is 70°C or higher and 350°C or lower.

The single crystal A thus formed has a good interface with the underlying Si and also has excellent surface properties.

After forming the single crystal An3 in the peer hole, the single crystal, 1
3 and the insulating film 2, a non-single crystal l (second Al) 4 is formed. In this case, a well-known deposition method other than the above-mentioned Aj2-CVD method can be used. Also, 1-CVD
When this method is used, ions and electrons are supplied by plasma to the insulating film 2, which is a non-electron-donating surface, or a surface modification process using plasma damage or ion implantation is applied to substantially eliminate electrons. It may be donor-like. By introducing the surface modification step in this manner, non-single crystal Al can be formed even on the insulating film 2 (FIG. 1(a)).

Thereafter, the non-single crystal Aff can be made into a single crystal by performing a heat treatment to be described later. This heat treatment may be performed at this point or after the insulating film 5 is formed.

Further, the heat treatment may be performed after the non-single crystal Al to be made into a single crystal is patterned into a desired wiring shape, or may be performed after being made into a single crystal.

As shown in FIG. 1(b), after patterning Al4, an insulating film 5 is formed. This insulating film 5 can be formed in the same manner as the insulating film 2 by a CVD method, a sputtering method, or the like.

In the manner described above, the single crystal A[wiring] can be formed.

In order to form a multilayer wiring, by repeating the same process again, a two-layer wiring structure of single crystal AI as shown in FIG. 1(c) can be obtained. If you repeat the same process further, you will get 3
A multilayer wiring structure such as a layer or four layers can also be obtained.

In FIG. 1(C), reference numeral 5 is an insulating film between the eyebrows, 6 is a selectively deposited single crystal 88ρ, 7 is a single crystallized 8β, and 8 is a protective insulating film.

The above is pure Al. In addition to this case, for example, AI containing a small amount of SAl in one film (AI-S
i) can also be made into a single crystal. In this case, when applying the above Al-CVD method, SiH+, 5i
A single crystal Al--Si seed can be formed by introducing a gas of a compound containing SAl such as J6 to form a film.

FIG. 2 shows an example of arrangement of single crystal Al seeds. Figure 2 (a
) is an example in which an opening of one side L1 is provided in a checker pattern in an insulator 11 formed on the surface of a semiconductor substrate, for example Si, and single crystal Al is selectively deposited within the opening. A non-single-crystalline film (not shown) is formed to cover the insulator] 1 and the single-crystal Al in the opening 12, and is heated to form a single crystal using the single crystal 88ρ as a seed.

Figure 2(b) shows -piece 1. ．． Fig. 2(c) shows an example in which the openings 11 with a width L- and the openings 12 with a width L4 are formed in a line & space pattern. An example is shown below. In either case, single crystal Al is selectively deposited within the opening,
A non-single crystal L film (not shown) is formed to cover the single crystal 88 and the insulator. The non-single crystal 1 film is heated to become a single crystal using the single crystal A as a seed.

Next, a heat treatment method for single crystallizing /l or A[-3Al will be described.

The basic steps are as follows. Figure 1(a).

A sample with a cross section like that shown in (b) is prepared and heated. Before and after the heat treatment, X-ray diffraction, conventional RHEED observation, and scanning μm RHEED microscopy were performed.

By heating, the second Aj, which is polycrystalline in the deposited state, is
2 becomes a single crystal because Al atoms are easy to flow (become
This is thought to be due to rearrangement of atoms. Conventionally, it has been known that a semiconductor having a covalent bond with Si, GaAs, etc. on an insulating thin film can be made into a single crystal by heat treatment. The AI or Al=Si thin film on the insulator thin film is about 4
It has been known that crystal grains with a grain size of several μm grow by heat treatment at 50°C, but in the present invention, if a single crystal Al region exists in the lower layer of A [or Aff-3i
It was discovered that 1 or Al--Si on an insulator can be single-crystalized over a large range of 0 μm or more.

The sample heating method is normal Hz, N2. Heat treatment using an electric furnace in an atmosphere of Ar or a mixture of these gases,
In addition to heating in a vacuum, methods such as heating with an instantaneous heating furnace (hereinafter abbreviated as RTA), laser heating, heating using a linear heater such as a carbon heater, high frequency heating, lamp heating, and electron beam heating are possible. be.

Generally, in LSI, Aff formed on Si,
Alternatively, the Aj2-Si thin film reacts with Si by heating, resulting in, for example, erosion of the Si substrate, AI, or i~Si.
This causes leakage of the Si p-n junction formed in the lower layer. Therefore, it is desirable that the heat treatment be performed at as low a temperature as possible. However, AI or AI-Si
In order for Aj2 to become single crystallized by heating, the Aj2 atoms must be able to flow due to thermal energy.

The heating method should be A [or 12-3i] as much as possible.
It is desirable that only the Si substrate under the Al or AI-Si be heated.

Heating in vacuum can be performed by a heater on the back side of the substrate in the scanning μm RHEED microscope shown in FIG.

In the case of heat treatment in vacuum, high vacuum is preferable in order to suppress large surface oxidation of Al. A high vacuum of about 1×1 O −6 Torr or less is desirable. In Figure 3, 2
0 is an electron gun, 21 is an electron beam, 22 is a diffracted electron beam, 2
3 is a fluorescent screen, 24, 24' and 24'' are optical fibers,
25.25' and 25'' are photomultiplier tubes, 26.26
' and 26'' Diffraction spot intensity signal converted into an electric signal, 27 is a scanning signal, 28 is a CRT, 29 is a secondary electron signal, 30 is a secondary electron detector, 31 is a sample, 34 is a vacuum chamber, 35 is an exhaust device.

A sample as shown in FIG. 1(a) is loaded into a vacuum chamber 34, and heated by a heater 32 from the back side of the sample 3. The temperature of the sample 31 is measured from the back side of the sample with a thermocouple 33. The heating method may be lamp heating or laser heating other than heater heating. The vacuum chamber 34 is evacuated by an exhaust device 35. The degree of vacuum in the vacuum chamber 34 before heating the sample is approximately 5×10-10 Torr.

The degree of vacuum during heating is approximately 5 x 10-” to 5 x 1O
-8 Torr. The higher the degree of vacuum, the better.
Even if the degree of vacuum is worse than the above, single crystallization by heat treatment is possible.

When the temperature measured by the thermocouple 32 is approximately 550° C. or higher, Al becomes single crystallized.

An instantaneous heating furnace (hereinafter abbreviated as RTA) to which the present invention can be applied will be described.

In RTA, only the wafer surface is heated in a short time, and the reaction between i or An-3i and the Si substrate can be reduced as much as possible.

An example of the configuration of the PTA device is shown in FIG.

200 is a base, and 201 is a base support. The base support is made of quartz and has claws 205 shown in FIG.
A base body 200 is placed on top of the base body 200 .

202 is a quartz tube. The cross section of the quartz tube 202 may be rectangular or circular. Alternatively, it may be made of metal such as stainless steel with a quartz window attached. 20
3 is a lamp which is linear. The light from the lamp 203 is reflected by the reflecting plate 204 and irradiated onto the base 200. The Aff deposition surface of the base body 200 faces the lamp side. A halogen lamp, tungsten lamp, Xe lamp, or Xe-Hg lamp can be used as the lamp. A halogen lamp with a fast heating rate was used in the RTA device.

The pressure inside the quartz reaction tube during heating may be either under reduced pressure or under atmospheric pressure. In addition, N2. Ar.

N2 or a mixture thereof can be used.

A N2 atmosphere is most desirable because it can be prepared manually with a high-purity gas containing the least amount of moisture and oxygen impurities.

In the RTA apparatus having the above configuration, single crystallization of Aff occurred when heated at a temperature of approximately 550° C. or higher. The temperature rise from room temperature to the heat treatment temperature takes approximately 5 to 30 seconds. The heat treatment time is about 10 seconds to 1 minute. There was no difference in the single crystallization region within the above temperature increase time and heat treatment time ranges.

It was necessary for the heating temperature to be approximately 550° C. or higher for single crystallization. Note that the substrate temperature was measured from the substrate surface using a radiation thermometer using PbS as a detector.

Next, laser heating to which the present invention can be applied will be explained.

Even in laser heating, it is possible to heat only the surface of the substrate, and the single crystallization region is wider than that of a PTA device.

Examples of lasers include argon ion laser (hereinafter referred to as Ar laser) with an output of several W to approximately 20W, crylene ion laser (hereinafter referred to as Kr laser) + He-Ne laser, C
02 laser, YAG laser, ArF or rF
Alternatively, an excimer laser such as XeF or XeCj2 can be used. The oscillation frequency is continuous oscillation,
Pulse oscillation of approximately 10 to 100 Hz may be used.

A feature of heating using a laser is that the single crystallized region can be enlarged by scanning the laser over the sample. Expansion of a single crystallized region by laser scanning will be explained.

Figure 5 fa) or (b), Figure 6 (a) or (
b) or the first A! on the semiconductor substrate 61 as shown in FIG. 7(a) or (b). 62 is formed with a width LIO,
A sample in which the second Al63 was formed over the entire surface of the substrate was used. Second 1! , 63, an insulating film 65 may be formed over the entire surface as shown in FIG. 5(b) or FIG. 6(b). Alternatively, as shown in FIGS. 7(a) and 7(b), the insulating film 66 may be formed in a stripe shape substantially perpendicular to the first i 62 line.

A laser beam 67 is applied to the above sample in FIGS. 5(a) and 5(b).
) or repeatedly scan as shown by line 68 in FIG. 7(a), or as shown in FIG.
Scanning is performed in one direction as shown by an arrow 69 in FIG. 6(b). The laser beam in Figures 5(a), (b) or 7(a) is a continuous wave Ar laser or a pulsed XeC laser beam.
A excimer laser is focused to approximately 20 to 100 μm.

In the case of FIG. 6(a), (b) or FIG. 7(b), for example, the optical system 70 using a cylindrical lens
The laser beam that is focused into a circular shape is transformed into a parallel beam 71.
Make it.

The scanning direction of the laser beam or parallel laser beam is as shown in FIG. 5(a) or (b), or FIG. 6<a) or (b), or FIG. 7(a) or (b). Scanning is performed in a direction approximately perpendicular to the line of Ar2.62.

Approximately 7,000 thermally oxidized 5i (h) were formed on the Si substrate, and the line width for the first Al262 was approximately 10 μm, and the line width for the second Al262 was approximately 10 μm.
In a sample as shown in FIG. 6(a), which has a thickness of 163 mm and about 5,000 people, a parallel Ar laser beam 71 is scanned over the sample in one direction (69) at a speed of about 1 cm/sec. Do not heat the back side of the sample.

The output of the Ar laser is approximately 20 to 50 W, and the laser power density on the back surface of the sample is approximately 50 to 200 KW/cm2. The laser heating atmosphere is an H2 gas atmosphere at 1 atmosphere.

Note that the substrate temperature is measured by measuring the temperature of the laser irradiated part with a radiation thermometer used as a PBS detector. When the substrate temperature is approximately 500° C. or higher, Al on the first insulating film can be made into a single crystal.

Next, a heating method using a linear heater to which the present invention can be applied will be explained.

FIG. 8 is a diagram for explaining a heating method using a linear heater. The heating substrate 82 is placed on the heating substrate support 81 . The heating support stand 81 is made of carbon. A linear heater 83 is placed on the heating base 82 . The linear heater 83 is also made of carbon, and is energized from the electric wire a, 84. The heating support table 81 is also heated by a heater (not shown) attached to the back surface of the heating support table. Further, the linear heater 83 moves in the direction of the arrow 85.

The heating atmosphere pressure does not depend on the pressure, ranging from atmospheric pressure to vacuum. H2, N2. An atmosphere of Ar or a mixed gas thereof is desirable. Although single crystallization occurs under vacuum, the device configuration is easier under atmospheric pressure.

A second 8ρ single crystallization occurs in the area directly below the linear heater. By heating with such a linear heater, the second Aj2 becomes a single crystal at a temperature of the substrate immediately below the linear heater of approximately 550° C. or higher. Note that the substrate temperature is measured with a radiation thermometer using PbS.

A feature of the heating method using a linear heater is that, like heating using a laser, the heating area can be scanned to enlarge the single crystallization area.

Next, a heating method using a lamp to which the present invention can be applied will be explained.

FIG. 9 is a diagram for explaining a heating method using a lamp. The heating substrate 92 is placed on the heating substrate support 91 . The heating support stand 91 is made of carbon. lamp 9
3 is a mercury lamp, a Hg-Xe lamp.

A Xe lamp, a Xe flash lamp, etc. can be used. Preferably, the lamp has a linear structure.

The light from the lamp 93 is focused by a reflecting mirror 94 so as to form a line on the surface of the substrate. The heating support table 91 is also heated by a heater (not shown) attached to the back surface of the heating support table. Further, the heating region 95 moves in the direction of an arrow 96 on the heating substrate due to the movement of the lamp. The heating atmosphere pressure does not depend on the pressure, ranging from atmospheric pressure to vacuum. Hz, N2. An atmosphere of Ar or a mixed gas thereof is desirable. Although it forms a single crystal even under vacuum,
The device configuration is easier under atmospheric pressure.

Second Al single crystallization occurs in the linearly heated region,
The second 8β becomes a single crystal when the substrate temperature in the heating region 95 is approximately 550° C. or higher. Note that the substrate temperature is Pb
Measure with a radiation thermometer using S.

Next, a heating method using high frequency heating to which the present invention can be applied will be explained.

FIG. 10 is a diagram for explaining a heating method using high frequency heating. The heating substrate 103 is placed on a heating substrate support. 101 is a support made of carbon. Moreover, 102 is a plate made of quartz arranged at intervals.

As shown in FIG. 1O, the heating support table on which the substrate is placed is heated by a high frequency coil (not shown) provided around the heating support. Since the quartz plate 102 is not heated by high frequency, a portion 104 on the base is heated to the highest temperature.

As the wafer moves in the direction indicated by arrow 105, region 104 heated to a high temperature also moves on the wafer. The heating atmosphere pressure was independent of pressure, ranging from atmospheric pressure to vacuum. 82. To prevent oxidation of the A42 surface. Nz
, Ar, or a mixed gas atmosphere thereof is desirable. Although single crystallization occurs under vacuum, the device configuration is easier under atmospheric pressure. In the following examples, the atmospheric pressure is atmospheric pressure.

Single crystallization of the second Al1 occurs in the linearly heated region 104, and the second Al1 can be single crystallized at a substrate temperature of approximately 550° C. or higher in the heated region 104.

Note that the substrate temperature is measured with a radiation thermometer using PbS.

A heating method using an electron beam to which the present invention can be applied will be explained.

FIG. 11 is a diagram for explaining a heating method using an electron beam. Electron beam 1 from filament 112
13, a focusing coil 115, a scanning coil, and a deflection plate 115;
', the light is focused linearly on the heating base 111. On the substrate, a portion 1140 is linearly heated to a high temperature. As the wafer moves in the direction indicated by arrow 116, region 114 heated to a high temperature also moves over the wafer.

/1 In order to suppress oxidation of the surface, the heating atmosphere pressure is preferably a high vacuum. Al1 becomes single crystallized at a vacuum degree of about 10-' Torr or less. The speed of movement of the substrate is 0.5-10 cm per minute. The substrate surface temperature in the heating region is measured with a radiation thermometer using PBS, and when the temperature is approximately 450° C. or higher, Al can be single crystallized.

A method of observing a single crystal region using the scanning μm RHEED microscope shown in FIG. 3 will be described.

The scanning μm RHEED microscope is ExtendedA
bstructs of the 21st Conf
erence on 5solidState Devi
ces and Materials (1989) p.
, 217 and Japanese Journal o
f Applied Physics vol.

28, No. 11 (1989) L2075. This is the method disclosed in . Conventional RHEED (Reflecti
on High Energy Electron Di
In the ffraction (reflection high-speed electron diffraction) method, an electron beam is incident on the sample surface at a shallow angle of 2 to 3 degrees, and the crystallinity of the sample surface is evaluated from the diffraction pattern generated by the diffraction electron beam. However, the electron beam diameter is
Since the thickness ranged from 100 μm to several hundred μm, only average information about the sample surface could be obtained. The scanning μm RHEED microscope shown in FIG. 3 can narrow down the electron beam diameter from the electron gun 20 to 0.1 um and observe the electron beam diffraction pattern from a specific micro region on the sample surface on the fluorescent screen 23. . In addition, the electron beam 21 is two-dimensionally scanned over the sample surface, the diffracted electron beam 22 is guided to the fluorescent screen 23, and the intensity change of arbitrary diffraction spots on the diffraction pattern is detected as an image signal 26.
．． 26', 26~ are used to obtain a two-dimensional image (scanning μm RHEED image) of the sample surface due to changes in the intensity of diffraction spots.
can be obtained on a CRT28. At this time, when observing a scanning μm RHEED image using different diffraction spots A and C on the diffraction pattern as shown in Figure 12, it is found that even if the lattice planes parallel to the sample surface are aligned (100), for example, the in-plane With this method, rotating grain boundaries can be distinguished and visualized. Here, the diffraction spot A is a diffraction spot on a line (line C) that is perpendicular to the plane where the diffraction pattern occurs and the sagittal plane formed by the incident electron beam, and the diffraction spot C is a diffraction spot that is not on the line β. be. As shown in Fig. 13, although the lattice plane parallel to the sample surface is (100), for example, the crystal grain
When the crystal grains X and y rotate within the plane of each other, in the scanning μm RHEED image using the diffraction spots A, both the crystal grains X and y are displayed as regions with strong intensity. On the other hand, in the scanning μm RHEED image using the diffraction spots C, only the crystal grains X are displayed as regions with high intensity. Therefore, scanning μmRHEE using line spots A and C as shown in FIG.
By observing the D image, it is possible to identify whether the crystal in the observed region is a polycrystal with in-plane rotation or a single crystal.

Next, an example of single crystallization of Al on SiO□ by heat treatment will be described.

The sample will be explained.

The single crystal seed pattern is as shown in FIG. 2 described above. That is, in the case of a checker pattern as shown in FIG. 2(a), the size of the hole is set to 0.5 μm to 20 μm, and in the case of a peer hole pattern as shown in FIG. 2(b), L3 is set to 20 μm. In the case of a line and space pattern as shown in Figure 2 (C), L8 is 20.
It is set to be less than μm. Then, a sample in which non-single crystal Al was formed on such a single crystal seed pattern was prepared.

When this sample was evaluated by X-ray diffraction method, AI! ,(
ill) peak was observed. Also, the electron beam diameter is 1
When the electron beam diffraction pattern was observed using a conventional RHEED device with a diameter of 00 μm to 1 mm, a ring-shaped pattern as shown in FIG. 14(a) was observed.

Therefore, it was found that the A[ deposited on the entire surface was a (111) oriented polycrystal.

However, although the above X-ray diffraction and conventional RHEED observation confirm that it is polycrystalline, the size of the crystal grains is unknown. When the electron beam diffraction pattern was observed using a scanning μmRHEED microscope using an electron beam focused to 0.1 μmφ, a spot pattern as shown in FIG. 14(b) was observed although the intensity was weak. FIG. 15(a) shows the result of observing a scanning μm RHEED image using the intensity of the diffraction spots on the spot-like diffraction pattern. The shaded areas are areas with strong diffraction spots, and the white areas are areas with weak diffraction spots.

Based on the size of the shaded area, the grain size is approximately several to 10
It can be seen that it is on the order of μm.

The same sample was incubated at 550°C in a scanning μ-RHEED microscope.
, After heating for 15 minutes, electron diffraction pattern and scanning μm
RHEED images were observed. In the electron beam diffraction pattern, a spot pattern as shown in FIG. 14(b) was observed, which had a stronger intensity than before heating. The diffraction pattern in FIG. 14(b) shows the [101
] It was found that this is a diffraction pattern that occurs when an electron beam is incident from the direction.

Diffraction spots A (11
The results of observing the scanning μm RHEED image using the intensities of diffraction spots C (1 diffraction spot) and diffraction spot C (202 diffraction spots) are the first
5 (b) and (C). Diffraction spots A and C were both strong at any position on the sample surface, and it was confirmed that the entire observation area was a single crystal. That is, Si
It was confirmed that even if a β thin film is formed on O□, if single crystal AΩ is present in the Al lower layer, it becomes single crystallized by heat treatment. When the sample after heat treatment was evaluated using an X-ray diffraction device,
Only the (111) peak was observed, and the conventional RHEE
When the electron beam diffraction pattern was observed using a D device, a spot pattern indicating a single crystal was observed as shown in FIG. 14(b).

Next, single crystallization was observed using another sample. In this sample, as shown in FIG. 16(a), a 1 μm thick silicon oxide film was formed on a Si substrate by a thermal oxidation method, and this silicon oxide film was etched with S by dry etching.
An opening (Si opening) is opened to expose the i surface.

In the area (I) of FIG. 16(a), there is the area shown in FIG. 2(a).

A checker pattern, a pier hole pattern, or a line and space as shown in (b) and (c) is formed. In area (II), the above-mentioned checker pattern, peer hole pattern or line &amp;
A region where no space is formed, that is, the entire SiO
□ is the area. As shown in Figure 16(a), 5iO
On the substrate patterned with z, the first 8ρ is selectively deposited only on the Si openings by CVD using DMAH and H, and after the surface modification step, the second AfAl is deposited on the substrate. It was deposited all over the surface.

After depositing Aj2, it was evaluated by X-ray diffraction method and found to be 1.1 (
111) Only the peak was observed. Further, when the electron beam diffraction pattern was observed using an EED apparatus (conventional R) with an electron beam diameter of 100 μm to 1 mmφ, a ring-shaped pattern as shown in FIG. 14(a) was observed.

Therefore, it was confirmed that the A deposited on the entire surface was a (111) oriented polycrystal. Next, scanning μRHEED
When the electron beam diffraction pattern was observed using a microscope using an electron beam narrowed down to 0.1 μm, a spot pattern as shown in FIG. 14(b) was observed although the intensity was weak. Figure 15 (
As shown in a), it was polycrystalline consisting of crystal grains of several to 10 μm.

The sample was scanned at 645°C in a scanning μmR) IEED microscope.
, after heating for 15 minutes, electron diffraction pattern, and scanning μ
mRHEED images were observed. In the electron beam diffraction pattern, a spot pattern as shown in FIG. 14(b) was observed, which was stronger in intensity than before heating. The diffraction pattern shown in FIG. 14(b) was found to be a diffraction pattern generated when an electron beam was incident on the Al (111) surface from the [101] direction from the position where the diffraction spots appeared. Figure 14(b)
Scan μ using the intensities of diffraction spots A (111 diffraction spots) and diffraction spots C (202 diffraction spots) on the diffraction pattern of
The results of observing the mRHEED images are shown in Figure 16 (b) and (
c). In FIGS. 16(b) and 16(c), the shaded areas are regions with strong diffraction spots. Figure 16(b)
, (c) The region with high intensity is a (111) single crystal. Figure 16(b) and (It was found that the region single crystallized from cl was approximately 1104z from the region (1) where the Si opening was formed. That is, by heat treatment, there was no Si exposed part in the Al lower layer. (It was confirmed that single crystallization occurred up to a distance of approximately 10 μm from the region (I) where the pattern was formed.

The patterns formed in area (I) are (a) checker pattern, (b) pier hole pattern, (C
) For both line & space patterns, the area (
A single crystal was formed over a range of about 10 μm from I).

When the SiO□ thickness was 500 to 1 μm, the region that became single crystallized by heat treatment was the same as that shown in FIGS. 16(b) and 16(c), regardless of the SiO2 thickness. Further, even when the thickness of the Al film deposited on the entire surface of 5i02 was 500 to 1 μm, the region where single crystallization occurred was similar to that shown in FIGS. 16(b) and 16(c).

The single crystallization area in the case of a heating method in which the heating area on the substrate moves, such as laser heating, heating high frequency heating using a linear heater, or electron beam heating, was measured as follows.

The area (IIT) in FIG. 17(a) includes the region (IIT) in FIG. 16(a).
Similar to area (I), a checker pattern, a pier hole pattern, and a line & space pattern are formed.
A first insulating film is formed in region (IV) of FIG. 17(a). The first Al and the second /
l is formed.

In the deposited state, the second Al has a grain size of several to 10 μm.
It is polycrystalline.

A laser beam as shown in FIG. 5 scans in the χ direction in FIG. 17(a). Furthermore, when a flat parallel laser as shown in FIG. 6 is used, the heating region is moved in the χ direction in lamp heating, RF heating, and electron beam heating.

The results of observation using a scanning μ-RHEED microscope after the heat treatment are shown in FIGS. 17(b) and 17(c). Scanning μmRH
In the electron beam diffraction pattern obtained using an EED microscope, a spot pattern as shown in FIG. 14(b) was observed, which was stronger in intensity than before heating. Diffraction spots A (111 diffraction spots) and diffraction spots C (
17(b) and (c).
) A scanning μm RHEED image was observed. The shaded area indicates a region with strong diffraction spot intensity. Diffraction spots A and C
A region in which both of these are strong is a (111) single crystal region.

In FIG. 17(c), by measuring the distance L8, it is possible to know the region that has become single crystallized by heating.

Note that FIG. 17(a) is similar to FIG. 17(b) and (c).
In the above sample, only one first Al layer exists in region (III). Further, the moving direction of the heating region is the χ direction in FIG. 17fa). Although L8 is shown as approximately 10 μm in FIG. 17(c), L8 reached approximately 1 cm in samples subjected to laser annealing, linear heater heating, lamp heating, RF heating, and electron beam heating.

That is, it was confirmed that the heat treatment caused no Si exposed portion in the lower layer of Aj2 (in other words, a portion approximately 1 cm away from the region where the pattern was formed was formed into a single crystal).

Electromigration resistance of Al on single crystallized SiO□ was measured. A [or AA-3i wiring by conventional sputtering method, 250°C, l
Under the current test of 06A/cm2, the wiring cross-sectional area is 1μm2
In this case, an average wiring life of about 1×10 2 to 10 3 hours was obtained. On the other hand, in the above test, the single crystal 1 arrangement based on the present invention had a wiring with a cross-sectional area of 1 μm2.
A wiring life of 10' hours was obtained. Also, the wiring width is 0.8
In the above test, an average wiring life of 103 to 104 hours was obtained even in a wiring having a thickness of 0.3 μm.

Further, a single crystallized 8β was processed into a width of approximately 1 μm, a silicon nitride film was deposited by plasma CVD, and stress was applied for 1000 hours at an ambient temperature of 150° C., and the rate of disconnection was measured. For wiring with a length of 1+nm, conventional sputtering Aj2 has a disconnection rate of 1 for 1000 lines.
In contrast, in the single crystal Al according to the present invention, no disconnection occurred in 1000 lines.

In other words, it was possible to significantly improve the EM and SM palpitation resistance by disposing one single crystal.

(Example 1) First, the method for preparing the sample to be measured is as follows. The cross-sectional shape of the sample is shown in FIG. 1(a).

Hydrogen combustion method (H2: 4℃/min, 0
2: 2°C/m1n) at a temperature of 1000°C. The plane orientation of the Si wafer is (ioo) and (1
11) was used. A photoresist was applied to the entire Si wafer, and a desired pattern was printed using an exposure machine.

After developing the photoresist, reactive ion etching (R
IE), etc., using a photoresist as a mask to remove the underlying 5i.
O7 was etched to partially expose the Si surface.

Next, 11 films were deposited on the Si wafer by low pressure CVD. Dimethylaluminum hydride and hydrogen were used as raw material gases. The deposition temperature is approximately 270° C., and the pressure inside the reaction tube during deposition is approximately 1.5 Torr. First, An (first i) is selectively deposited only on the exposed surface of the Si surface, and a surface modification process is performed when the l film thickness becomes the same as the 5in2 film thickness. Al) was deposited on the entire surface of the Si wafer. As a surface modification step, plasma was generated in a low pressure CVD apparatus.

5102 pattern shape formed on the measured sample, An
The film thickness is as follows. SiO□ film thickness is 1000
There are five types: 2,500 people, 5,000 people, 7,500 people, and 10,000 people. The pattern formed on the Si wafer is checked by the checker shown in Fig. 2(a).
It's a pattern.

The checker size L1 is 0.25.0.5,1.
There are eight types: 2°3, 5, 10, and 20 μm. The thickness of Al deposited on the entire surface of the wafer (second Al, 4 in Figure 1) is 1000, 2500, 5000,
There are five types: 7,500 people and 10,000 people. The scanning μmR sample prepared through the above steps is shown in Figure 3.
It was loaded into a HEED microscope, and electron beam diffraction pattern observation and scanning μ-RHEED image observation were performed. Then, the heater was energized to heat the sample, and the electron beam diffraction pattern and scanning μm RHEED image were observed again. Scanning μmR)I
The conditions for heating with the EED microscope were (1) 550°C, 6 hours, (2) 600°C, 2 hours, (3) 645°C, 15
(4) 670°C for 5 minutes, and (5) 700°C for 5 minutes.

After depositing Aj2 and before loading it into a scanning μm RHEED microscope, it was evaluated by X-ray diffraction, and all samples showed a 1 (111) peak regardless of the SiO□ film thickness, checker size, and second Al film thickness. only was observed. Further, when electron beam diffraction patterns were observed using a conventional RHEED device with an electron beam diameter of 100 μm to 1 mmφ, a ring-shaped pattern as shown in FIG. 14(a) was observed in all samples. Therefore, it was deposited on the entire surface. It was confirmed that l was a polycrystal with a (1,11) orientation.

Scanning μ-R) (Load the sample on the EED microscope and
When the electron beam diffraction pattern was observed using an electron beam narrowed down to m, the intensity was weak but as shown in Figure 14(b).
A spot pattern as shown in is observed. Scanning using the diffraction spot intensity on the spot-like diffraction pattern μmR)
When the IEED image was observed, it was found to be polycrystalline, consisting of crystal grains of several to 10 μm, as shown in FIG. 15(a).

Then, in a scanning μ-RHEED microscope, the 5
After a standard heat treatment, an electron diffraction pattern and a scanning μm RHEED image were observed. Si rawe plane orientation,
Regardless of the 5i02 film thickness, checker size, or second Al2 film thickness, the electron beam diffraction pattern of all samples was stronger than that before heating, and a spot pattern as shown in Figure 14(b) was observed. It was done. The diffraction pattern shown in FIG. 14(b) was a diffraction pattern generated when an electron beam was incident on the Al (111) surface from the [101) direction from the position where the diffraction spots appeared. Diffraction spots A (111 diffraction spots) and diffraction spots C (20
The results of observing a scanning μm RHEED image using the intensity of 2 diffraction spots) were similar to those shown in FIGS. 15(b) and (c). In FIGS. 15(b) and 15(c), the shaded areas are regions with strong diffraction spots. In the Aff film deposited on the observed checker pattern, both diffraction spots A and C
Both were strong, and it was confirmed that they were single-crystalized by heat treatment. When the electron beam diffraction patterns of the heat-treated samples were observed using a conventional RHEED apparatus, spot patterns indicating single crystals as shown in FIG. 14(b) were observed in all samples.

In heat treatment under two conditions: 670° C. for 5 minutes and 700° C. for 5 minutes, the A film on 5 iOz became single crystal, but non-uniformity occurred in the thickness of the A4 film after the heat treatment. In addition, after heat treatment, photoelectron spectroscopy (ESCA), Auger electron spectroscopy (A
When the depth distribution was measured by ES), it was found that SiO□
At the second, l interface, a solution of l, Si, and O was observed. Moreover, single crystallization did not occur in heat treatment at 500° C. for 6 hours.

(Example 2) A sample having a cross section as shown in FIG. 1(a) was prepared in the same manner as in Example 1, and the sample was loaded into a scanning μm RHEED microscope and heat-treated.

The difference from Example 1 is the pattern shape formed on the Si wafer. The pattern on the Si wafer is shown in Figure 2 (b).
) is the peer hole pattern shown in

The size L2 of the peer hole is 0.25.0.5.1,
5 types of 25μm, A3: 1, 2, 5, 10.20g
There are five types of m. Al. 25 can be made by combining A3
Various types of pier hole patterns were formed. 5iCh film thickness,
Al2 deposited on the entire surface of the wafer (second Al in Fig. 1, 4
) is the same as in Example 1.

The sample prepared through the above steps was heat-treated and observed in the same manner as in Example 1. The heat treatment conditions for the sample were also the same as in Example 1.

As in Example 1, X-ray diffraction before sample heat treatment, conventional RHE
Electron beam diffraction pattern observation using ED device, scanning μmRH
Electron diffraction pattern and scanning μmR by EED microscope
From HEED image observation, the Aff (second Al2) deposited on the entire surface was found to be (111)-oriented polycrystals consisting of crystal grains of several to 10 μm in size in all samples.

Then, in a scanning μm RHEED microscope, the 5
After performing the standard heat treatment, the electron beam diffraction pattern and scanning, -R1 (When observing the EED image, Example 1
Similarly, regardless of the Si wafer surface orientation, 5102 film thickness, pier hole dimensions, and second Al2 film thickness, the electron diffraction pattern of all samples is stronger than that before heating.
A spot pattern as shown in Figure (b) was observed.

Diffraction spots A (11
When scanning μm RHEED images were observed using the intensities of diffraction spots (1 diffraction spots) and diffraction spots C (202 diffraction spots), the same scanning μ as in FIGS. 15(b) and (c) was observed, as in Example 1.
mRHEED images were observed. In other words, in the Al film deposited on the pier-hole pattern, the diffraction spots A
It was confirmed that both C and C were formed into single crystals by heat treatment.

As in Example 1, the l film on 5i02 was made into a single crystal by the heat treatment under the conditions of 670°C for 5 minutes and 700°C for 5 minutes, but the film thickness became non-uniform during the heat treatment. was. In addition, after the heat treatment, the depth distribution was measured by photoelectron spectroscopy (ESCA) and Auger electron spectroscopy (AES), and it was found that SiO□ and the second A! At the interface of Al and Si,
A solution of 0 was observed. Moreover, single crystallization did not occur in heat treatment at 500° C. for 6 hours.

(Example 3) A sample having a cross section as shown in FIG. 1(a) was prepared using the same procedure as in Example 1, and the sample was loaded into a scanning μmR1 (EED microscope) and heat-treated.

The difference from Example 1 is the pattern shape formed on the Si wafer. The pattern on the Si wafer is shown in Figure 2 (c
) is the line and space pattern shown in the figure. Line & space size L4 is 0.25.0.5i, 2.5g
5 types of m, L5 of 1, 2, 5° 10, 20 μm
It is a kind. L4. 25 types of line and space patterns were formed by combining L5. SiO□ film thickness,
Al deposited on the entire surface of the wafer (second, l, 4 in Fig. 1)
The thickness is the same as in Example 1. The sample prepared through the above steps was heat-treated and observed in the same manner as in Example 1. The heat treatment conditions for the sample were also the same as in Example 1.

As in Example 1, X-ray diffraction before sample heat treatment, conventional RHE
EI) Electron beam diffraction pattern observation using equipment, scanning μmR
Electron diffraction pattern & scanning μm by HEED microscope
From observation of RHEED images, the Al (second 8 ρ) deposited on the entire surface was (111)-oriented polycrystalline consisting of crystal grains of about several to 10 μm in all samples.

Next, after performing the five levels of heat treatment shown above in the scanning μmR1 (EED microscope), the electron beam diffraction pattern and the scanning μmR1 (E E D image were observed. As in Example 1, the Si wafer was Regardless of the plane orientation, 5102 film thickness, line and space dimensions, and the second i film thickness, the electron beam diffraction pattern of all samples was stronger than before heating, as shown in Figure 14 (b). A spot pattern was observed. Diffraction spots A (
When the scanning μ-RHEED image was observed using the intensities of diffraction spots C (111 diffraction spots) and diffraction spots C (202 diffraction spots),
As in Example 2, scanning u-RHEED images as shown in FIGS. 15(b) and 15(c) were observed. i.e. line &
In the L film deposited on the space pattern, both diffraction spots A and C were strong, and it was confirmed that the film was made into a single crystal by the heat treatment.

Same as Example 1, 670°C for 5 minutes and 700°C15
In the heat treatment for two minutes, the Al film on 5i02 became single crystallized, but after the heat treatment, the thickness of the +1 film was non-uniform. In addition, after the heat treatment, when the depth distribution was measured by photoelectron spectroscopy (ESCA) and Auger electron spectroscopy (AES), it was observed that the solution of Al, Si, and O appeared at the interface between SiO□ and the second Al. It was done. Moreover, single crystallization did not occur in heat treatment at 500° C. for 6 hours.

(Example 4) A sample having a cross section as shown in FIG. 1(a) was prepared in the same manner as in Example 1, and the sample was loaded into a scanning μ-RHEED microscope and heat-treated.

The difference from Example 1 is the pattern shape formed on the Si wafer. The pattern on the Si wafer will be explained. As shown in FIG. 16(a), in area (1), 5
An opening is formed in iCh, but in region (n),
There are many Si openings (5i02) formed on the entire surface.The pattern formed in region (I) is shown in Fig. 2(a).
Checker patterns shown in (b) and (c),
They are a pier hole pattern and a line & space pattern. The dimensions L1 of the checker are 0.250.5, 1, 2,
There are 6 types of 3.5um. There are five types of pier hole size L2: 0.25, 0.5, and 1.2.5 gm, and three types of pier hole size L3: 1 and 2.5 μm. L2. Fifteen types of pier hole patterns were formed by combining L.

The line & space size L4 is 0.25.0.5.
There are four types of 1 and 2 gm, and three types of L and 12.5 μm. Twelve types of line and space patterns were formed by combining L, L, and L. SiO□ film thickness, An deposited on the entire wafer surface (the second eight ρ in Fig. 1(a),
The thickness of 4) is the same as in Example]. The sample prepared through the above steps was heat-treated and observed in the same manner as in Example]. The heat treatment conditions for the sample were also the same as in Example 1.

As in Example 1, X-ray diffraction before sample heat treatment, conventional RHE
Electron beam diffraction pattern observation using ED device, scanning μmRH
Electron diffraction pattern and scanning μ-R by EED microscope
) (From EED image observation, i deposited on the entire surface (second,
l) is several to 1. O(t
It consisted of crystal grains of about m (11111 oriented polycrystal).

Then, in a scanning μm RHEED microscope, the 5
After the standard heat treatment, the electron beam diffraction pattern and scanning μ-RHEED image were observed, and as in Example 1, the surface orientation of the Si wafer, the 5i02 film thickness, and the pattern formed in region (I) were observed. Irrespective of the shape and dimensions and the thickness of the second Al film, the electron beam diffraction pattern of each sample was observed to be a spot pattern with a stronger intensity than before heating, as shown in FIG. 14(b). Diffraction spots A (111 diffraction spots) and diffraction spots C (2
When the scanning μmR) (EED image was observed using the intensity of the 02 diffraction spots), the scanning μR1 (EED image) similar to that shown in Fig. 16(b) and (c) was observed. The region where both diffraction spots A and C are strong is the (111) single crystal region.
Similar to b) and (C), the single crystallized region is approximately 10 μm from the region (I) where the opening is formed (Fig. 16(C)
), it was found that the area indicated by L6).

That is, even if there is no Si exposed part in the lower layer part 12 due to heat treatment, the area (I) where the pattern is formed is approximately 1101
It was confirmed that single crystallization occurred up to a distance of t.

As in Example 1, the /l film on SiO□ became single crystal when heat treated under two conditions: 670°C for 5 minutes and 700°C for 5 minutes, but the thickness of the i film became non-uniform after the heat treatment. was.

In addition, after the heat treatment, when the depth distribution was measured by photoelectron spectroscopy (ESCA) and Auger electron spectroscopy (AES), it was observed that the solutions of i, Si, and 0 appeared at the interfaces of 5102, 2nd, and 11. It was done. Furthermore, heat treatment at 500° C. for 16 hours did not cause single crystallization.

(Example 5) In Examples 1, 2.3, and 4, 8102 made by thermal oxidation was used as the insulating film. In this example, the insulating film was 5iOz (hereinafter referred to as CVD) formed by normal pressure CVD.
5102), a poron-doped oxide film (hereinafter referred to as BSG) formed by the atmospheric pressure CVD method, a phosphorus-doped oxide film (hereinafter referred to as PSG) formed by the atmospheric pressure CVD method, The formed boron and phosphorus doped oxide film (hereinafter abbreviated as BPSG),
Nitride film formed by plasma CVD method (hereinafter referred to as P-3)
iN), thermal nitride film (hereinafter referred to as T-5iN), thermal nitride film formed by low pressure CVD method (hereinafter referred to as LP-5i)
(abbreviated as N), a nitride film (abbreviated as N), formed by an ECR device (
Examples 1, 2,
A sample similar to 3.4 was prepared and subjected to X-ray diffraction and conventional RHEE.
Electron beam diffraction pattern observation using D device, scanning μ-RH
The sample was loaded into an EED microscope, subjected to heat treatment, and an electron beam diffraction pattern and a scanning μ-RHEED image were observed. The thickness of the insulating film was approximately 5000. Note that thermal nitride film (T
-5i, N) was approximately 100 people thick. The thickness of the second Al film was approximately 7,500. The formed pattern shape is the same as in Examples 1.2 and 3.4.

The results obtained were similar to Examples 1, 2, and 3.4.

(Example 6) In Examples 1, 2, 3, and 4.5, both the first Al and the second Al were CVDA ff films formed by low pressure CVD. In this example, the second Al was formed by sputtering. Conditions other than the second i are set in Examples 1, 2, 3, and 4.
The i-film was heat-treated in the same manner as in Example 5.

The results obtained were similar to Examples 1, 2, 3, 4.5.

(Example 7) In Examples 1, 2, 3, 4, 5.6, the first l and the second A! ! , both were pure i. In this example, Aj2-SAl was used instead of pure Al. Si in the film
The content is 0.2.0.58 and 1.0%.

The obtained results are in Examples 1, 2, 3, 4. ．． It was similar to 56.

(Example AI) A sample similar to that in Example 1 was prepared.

As in Example 1, X-ray diffraction before sample heat treatment, conventional RHE
Electron beam diffraction pattern observation using ED equipment, scanning μ-
Observation of the electron diffraction pattern and scanning μ-RHEED image using a RHEED microscope revealed that Al deposited on the entire surface (
The second Al1) is several to 10 in all samples.
It was a (111) oriented polycrystal consisting of crystal grains on the order of μm.

The above-mentioned sample was loaded into the RTA apparatus shown in FIG. 4, and heat-treated. The substrate temperature was measured at 450°C, 500°C, and 550°C using a radiation thermometer using PbS.

There are five levels: 600°C and 650°C. The heating time to the heat treatment temperature was 10 seconds, and the heat treatment times were 10 seconds and 20 seconds.

40 seconds and 60 seconds.

Next, in the scanning μ-RHEED microscope shown in FIG. 3, the electron beam diffraction pattern and the scanning μ-R
The HEED image was observed. Si wafer surface orientation, 5iO7
Regardless of the film thickness, checker size, and second Al1 film thickness, the electron beam diffraction pattern of all samples was observed to be a spot pattern with a stronger intensity than before heating, as shown in Figure 14(b). Ta. The diffraction pattern in FIG. 14(b) is from the position where the diffraction spot appears to A! (1,11) plane [10
1] This was a diffraction pattern generated when an electron beam was incident from the direction. Diffraction spot A on the diffraction pattern in Figure 14(b) (111 diffraction spots):! 3 and diffraction spot C(2
Scanning μmR1-IEED using the intensity of 02 diffraction spots)
The results of observing the images were similar to those shown in FIGS. 15(b) and (c). In FIGS. 15(b) and 15(c), the shaded areas are regions with strong diffraction spots. Diffraction spots A are observed in the eight-layer film deposited on the checker pattern.
Both C and C were strong, and it was confirmed that they were single-crystalized by heat treatment. When the electron beam diffraction patterns of the heat-treated samples were observed using a conventional RHEED apparatus, spot patterns indicating single crystals as shown in FIG. 14(b) were observed in all samples.

In the heat treatment at 650° C., the Al film on the SiO□ became single crystallized, but the thickness of the Aff film became non-uniform after the heat treatment. In addition, when the depth distribution was measured by photoelectron spectroscopy (ESCA) and Auger electron spectroscopy (AES) on the sample after heat treatment at 650°C, it was found that Al1, Si, and O are dissolved at the interface of 5102 and the second i. One exposed person was detected. Further, heat treatment at 500° C. or lower did not cause single crystallization.

(Example Al) A sample having the pier hole pattern shown in FIG. 2(b) was prepared in the same manner as in Example 2, and heat treated using an RTA apparatus. The pier hole size is the same as in the second embodiment.

The sample prepared through the above steps was heat-treated and observed in the same manner as in Example A1. The heat treatment conditions for the sample were also the same as in Example Al.

Similar to Example A1, X-ray diffraction before sample heat treatment, conventional RH
Electron beam diffraction pattern observation using EED device, scanning μmR
Electron diffraction pattern and scanning μm by HEED microscope
Observation of the RHEED image revealed that 1 (second i) was deposited on the entire surface.
) was a (111) oriented polycrystal consisting of crystal grains of several to 10 LLm in each sample.

Next, after heat treatment was performed using an RTA apparatus, the electron beam diffraction pattern and the scanning μm RHEED image were observed, and as in Example 1, the surface orientation of the S1 wafer, the 5102 film thickness, the pier hole dimension, and the second l film were observed. Irrespective of the thickness, the electron beam diffraction pattern of each sample was observed to be a spot pattern with a stronger intensity than before heating, as shown in FIG. 14(b). Diffraction spot A on the diffraction pattern in Figure 14(b)
When scanning μ-RHEED images were observed using the intensities of (111 diffraction spots) and diffraction spots C (202 diffraction spots), the same scanning μ-RHEED images as in FIGS. 15(b) and (c) were observed, as in Example A1. image was observed. That is, it was confirmed that in the i-film deposited on the surface where the pier-hole pattern was formed, both the diffraction spots A and C were strong (and were made into single crystals by the heat treatment).

Similar to Example AI, heat treatment at 650°C resulted in 5102
The above II film became a single crystal, but the thickness of the i film became non-uniform after the heat treatment. In addition, when the depth distribution of the sample after heat treatment at 650°C was measured by photoelectron spectroscopy (ESCA) and Auger electron spectroscopy (AES), it was found that 51
At the interface between 02 and the second Al, solutions of l, 81, and O were observed to emerge. Further, heat treatment at 500°C did not cause single crystallization.

(Example A3) A sample having the same line and space pattern as in Example 3 was prepared and heat treated using a PTA apparatus.

The sample was heat-treated and observed in the same manner as in Example AI. The heat treatment conditions for the sample were also the same as in Example A1.

Similar to Example AI, X-ray diffraction before sample heat treatment, conventional RH
Electron beam diffraction pattern observation using EED imaging, scanning μmR
1 (from the observation of the electron beam diffraction pattern using an EED microscope and the scanning μm RHEED image, it was found that 8β (second
Aj2) is several to 10 μm in all samples.
It was a (111.) oriented polycrystal consisting of crystal grains of about 100 degrees.

Then, in a scanning μ-RHEED microscope, the 5
After the standard heat treatment, the electron beam diffraction pattern and scanning μmR)IEED image were observed, and it was found that Example A1
Similarly, the surface orientation of the Si wafer, the 5iOz film thickness, the line &
Irrespective of the space dimensions and the second Al film thickness, the electron beam diffraction pattern of each sample was observed to be a spot pattern with a stronger intensity than before heating, as shown in FIG. 14(b). Diffraction spot A (
111 diffraction spot) and diffraction spot C (202 diffraction spot), the scanning μ-RHEED image was observed in step 2. As in Example A1, the same scanning as in FIGS. 15(b) and (c) was performed. , -RHEED images were observed. That is,
A deposited on the line and space pattern
In the L film, both diffraction spots A and C were strong (and it was confirmed that they had become single crystals due to heat treatment.

As in Example A1, the 650° C. heat treatment turned the He4 film on 5i02 into a single crystal, but after the heat treatment, the thickness of the I film became non-uniform. In addition, for samples after heat treatment at 650°C, photoelectron spectroscopy (ESCA) and Auger electron spectroscopy (AE) were used.
When the depth direction distribution of S) was measured, it was observed that the solutions of i, Si, and O were not solved at the interface between Sigh and the second Aj2. In addition, single crystallization did not occur during heat treatment at 500°C.

(Example A4) Figure 1(a) was prepared using the same procedure as in Example 1 or Example A1.
A sample with a cross section as shown in is prepared, and a scanning μ-R
The sample was loaded into a HEED microscope and heat treated.

The difference from Example A1 is the pattern shape formed on the Si wafer. The pattern on the Si wafer will be explained. As shown in FIG. 16(a), an opening is formed at 5 iOz in region (I), but in region (It)
There are no Si openings (SiO2 is formed over the entire surface). The pattern formed in region (I) is shown in Figure 2 (a).
), (b), and (c) are the checker pattern, pier hole pattern, and line & space pattern. The dimensions of the checker are 0.25°0.5.1
, 2, and 3.5 μm. The size L2 of the peer hole is 0.25.0.5, 1.2. There are five types of 5um, and three types of L3, 1 and 2.5μm. L,, L
15 types of pier hole patterns were formed by combining . Line and space size 4 is 0.25.
4 types of 0.5.1 and 2 um, L is 1°2.5μ
There are three types of m. L4. 12 made by combining Ls
Formed different line & space patterns. SiO□
The thickness of the 8β film deposited on the entire surface of the sea urchin 8 (Fig. 1(a),
The thickness of +l, 4) is the same as in Example A1. The sample prepared through the above steps was heat-treated and observed in the same manner as in Example A1. The heat treatment conditions for the sample were also the same as in Example A1.

Similar to Example A1, X-ray diffraction before sample heat treatment, conventional RH
Observation of electron beam diffraction pattern using EED device, scanning u −
Observation of the electron beam diffraction pattern and scanning μ-RHEED image using a RHEED microscope revealed that A [(second
In all samples, A[) was a (111) oriented polycrystal consisting of crystal grains of about several to 10 μm.

Next, after heat treatment was performed using an RTA apparatus, the electron beam diffraction pattern and scanning μ-RHEED image were observed, and as in Example A1, the surface orientation of the S1 wafer, Si, 0
Regardless of the thickness of the second film, the shape and dimensions of the pattern formed in region (I), and the thickness of the second i, the electron diffraction pattern of all samples is stronger than that before heating. (b)
A spot pattern as shown in is observed. When a scanning μm RHEED image was observed using the intensities of diffraction spots A (111 diffraction spots) and diffraction spots C (202 diffraction spots) on the diffraction pattern in FIG. 14(b), the results were as shown in FIG.
Scanning μmR) IEED images similar to b) and (c) were observed. The shaded area indicates a region with strong diffraction spot intensity. The region where both diffraction spots A and C are strong is the (111) single crystal region. Similarly to FIGS. 16(b) and (c), the single crystallized region is approximately 10 μm from the region (di) where the Si opening is formed (the region indicated by L6 in FIG. 16(c)). I understand. That is, by heat treatment,
It was confirmed that there was no Si exposed part in the lower layer part (both at a distance of about 10 μm from the region (I) where the pattern was formed) and that it was single crystallized.

As in Example 1, the Al film on SiO2 became single crystallized by the heat treatment at 650°C, but the film thicknesses of the A and f2 films became non-uniform after the heat treatment. In addition, when the depth distribution of the sample after heat treatment at 650°C was measured using photoelectron spectroscopy (ESCA) and Auger electron spectroscopy (AES), it was found that S
A solution of i, Si, and O was observed at the interface between in and second Aj2. Further, heat treatment at 500°C did not cause single crystallization.

(Example A5) Examples Al, Al. A3. A4. In the first insulating film, SiO□ formed by a thermal oxidation method was used. In this example,
SiO□ formed by normal pressure CVD as the first insulating film
(hereinafter abbreviated as CVD 5in2), boron-doped oxide film formed by atmospheric pressure CVD method (hereinafter abbreviated as BSG), phosphorus-doped oxide film formed by atmospheric pressure CVD method (hereinafter abbreviated as PSG), atmospheric pressure CVD method A boron- and phosphorus-doped oxide film (hereinafter abbreviated as BPSG) formed by a method, a nitride film (hereinafter abbreviated as P-3iN) formed by a plasma CVD method, a thermal nitride film (hereinafter abbreviated as T-3iN), a low pressure CVD method Thermal nitride film (hereinafter referred to as L
Examples AI, Al. A3. A4. A sample similar to that was prepared and observed by X-ray diffraction, electron beam diffraction pattern observation using conventional RHEED,
The sample was loaded into a scanning μmRHEED microscope, heat-treated, and an electron beam diffraction pattern and scanning μmRHEED image were observed. The thickness of the first insulating film was approximately 5000. Note that the thickness of the thermal nitride film (T-5iN) was approximately 100 mm. The film thickness of the second Aj2 was approximately 7,500. The formed pattern shapes were those of Example AI, Al. A3.
A4. It is similar to

The results obtained are similar to Example AI, Al. A3. A4. It was the same.

(Example A6) Examples Al, Al. A3. A4. In A5, both the first Al and the second l were β films obtained by low pressure CVD. In this example, the second A[ was formed by the sub-lid method. Conditions other than the second Al are Example AI.

Al A3 A4. The Aj2 film was heat treated in the same manner as A5.

The results obtained are as follows: Examples Al, Al. A3. A4. A5
．． It was the same.

(Example A7) Example AI, Al. A3. A4. A5. In A6,
The first i and the second l were both pure A[. In this example, Aff-3Al was used instead of pure Al. The Si content in the film is 0.2.0.5.1.0%.

The results obtained are similar to Example AI, Al. A3. A4. A5
．． It was the same as A6.

(Example A8) The cross-sectional structure of the sample in Examples A1 to A7 is as shown in Fig. 1 (
It looked like a). In Example A1-88, the first 8ρ and the second Ar1. After the deposition, a second insulating film 5 was formed as shown in FIG. 1(b), and then heat treatment was performed using an RTA apparatus. Conditions other than the cross-sectional structure are the same as Examples A1 to A7. The crystallinity of the second Al after heat treatment is determined by removing the second insulating film 5 and using a conventional R)lEE[] device, scanning μm.
Confirmation was performed using a RHEED microscope.

The insulating film 5 in FIG. 1(b) is made by atmospheric pressure CVD.
iO7, PSG, BSG, BPSG, plasma CV
Six types of silicon nitride films prepared using a D-method silicon nitride ULhcR apparatus were used. The film thickness is 1000, 3000, 5000, Igm for each film.
And so.

The results obtained were similar to Examples A1 to A7.

(Example Bl) A sample similar to that in Example 1 was prepared.

As in Example 1, X-ray diffraction before sample heat treatment, conventional RHE
Electron beam diffraction pattern observation using ED device, scanning μ-RH
Turning and scanning μ of electron beam diffraction using EED microscope
From mRHEED image observation, Aj2 (second Afi) deposited on the entire surface was several to 10 tons in all samples.
It was a (111) oriented polycrystal consisting of crystal grains of about Lm.

The above sample was laser heated in the following manner. The laser is a continuous wave Ar laser (oscillation wavelength path 488r+
m and 514.5 nm, oscillation output maximum 20 W). The beam diameters on the sample are approximately 20 μm, 30 μm, and 7
0tLm, logm. The scanning direction was repeated in one direction as shown in FIG. 5(a).

The repetition width of the beam scan was set to be the same as that of the beam system. The scanning speed of the laser beam is 0 paths per minute.
．． 5.1, 2 + 5 + 10 cm. The substrate surface temperature was measured with a radiation thermometer using PbS, and was approximately 450'C, 550°C, 600°C, 650°C, and 700°C.
It is C.

The temperature at the substrate surface varied depending on the laser beam diameter, laser output, and laser beam scanning speed.

The following results show that when the laser beam diameter, laser beam scanning speed, and scanning interval are given, the surface temperature is 450℃,
The laser output was changed to 550°C, 600°C, 650°C, and 700°C.

Laser heating was performed in a hydrogen gas atmosphere at atmospheric pressure.

After each of the above samples was heat-treated under the above laser heating conditions, an electron beam diffraction pattern and a scanning μm RF (EED image) were observed in a scanning μm RHE E D microscope.
Regardless of the wafer surface orientation, SiO□ film thickness, checker size, or second i film thickness, the sample surface temperature is 550°C or higher regardless of the laser beam diameter, scanning speed, or beam repetition width. In this case, a spot pattern as shown in FIG. 14(b) was observed in which the electron beam diffraction pattern was stronger in intensity than before heating. The diffraction pattern in FIG. 14(b) is shown on the Ar (111) plane from the position where the diffraction spot appears [1
This is a diffraction pattern generated when an electron beam is incident from the direction [01]. Diffraction spots A (111 diffraction spots) and diffraction spots C (202
The results of observing the scanning μm RHEED image using the intensity of the diffraction spots (diffraction spots) were similar to those shown in FIGS. 15(b) and (C).

In FIGS. 15(b) and 15(c), the shaded areas are regions with strong diffraction spots. In the Ar film deposited on the observation checker pattern, both diffraction spots A and C were strong, and it was confirmed that the Ar film was formed into a single crystal by heat treatment. When the electron beam diffraction patterns of the heat-treated samples were observed using a conventional RHEED device, it was found that the 14th
A spot pattern indicating a single crystal as shown in Figure (b) was observed.

That is, Aj2, which was polycrystalline in the deposited state, became a single crystal due to the laser heating. Note that when the substrate surface temperature is 650°C or higher, when the depth distribution is measured by Auger electron spectroscopy or secondary ion mass spectrometry,
Dissolution of Si and Ar was observed at the interface between the insulating film on the substrate surface and the second Ar.

(Example B2) A sample with a checker pattern was prepared in the same manner as in Example 2, and the thickness of Sigh film was 8ρ (second 2.4 in FIG. 1) deposited on the entire wafer surface. This is the same as in Example. Example B1 The sample prepared through the above steps
The samples were heat-treated and observed using the same procedure. The heat treatment conditions for the sample were also the same as in Example B1.

Similar to Example B1, X-ray diffraction before sample heat treatment, conventional RH
Electron beam diffraction pattern observation using EED device, scanning μmR
Electron diffraction pattern and scanning μ by HEED microscope
- From the RHE E D image observation, Aj2 deposited on the entire surface.
(Second 71) is several to 10 in all samples.
It was a (111) oriented polycrystal consisting of crystal grains on the order of μm.

Next, laser beam irradiation heat treatment was performed under the same conditions as in the previous example, and the electron beam diffraction pattern and scanning μmRHEED image were observed using a scanning μmRHEED microscope.
As in Example B1, all samples were processed regardless of the surface orientation of the S1 wafer, the 5in2 film thickness, the checker size, and the second 12 film thickness. When the surface temperature was 550° C. or higher, it was confirmed from scanning μm RHEED image observation that single crystallization occurred. Also, as in Example 1, the substrate surface temperature was 650°C.
In the above case, when the depth distribution was measured by Auger electron spectroscopy or secondary ion mass spectrometry, dissolution of Si and Ar was observed at the interface between the insulating film on the substrate surface and the second Aj2.

(Example B3) A sample having a cross section as shown in FIG. 1(a) was prepared in the same manner as in Example B1, and heat treated by laser heating.

The difference from Example B1 is the pattern shape formed on the Si wafer. The pattern on the Si wafer is shown in Figure 2 (
This is the line and space pattern shown in C). line&
The space sizes L4 and 15 are the same as in the third embodiment.

The sample prepared through the above steps was heat-treated and observed in the same manner as in Example B1. The heat treatment conditions for the sample were also the same as in Example B1.

Similar to Example B1, X-ray diffraction before sample heat treatment, conventional RH
Electron beam diffraction pattern observation using EED device, scanning μmR
Electron diffraction pattern and scanning μ by HEED microscope
From mRHEED image observation, A [(second A, ff) deposited on the entire surface is several to 10 μm in all samples.
It was a (111) oriented polycrystal consisting of crystal grains of about 100%.

Next, laser beam irradiation heat treatment was performed under the same conditions as in Example B1, and the electron beam diffraction pattern and scanning μmRHEED image were observed using a scanning μmRHEED microscope. As in Example B1, the surface orientation of the Si wafer was 5i02.
Regardless of the film thickness, line & space size, and second Ar film thickness, for any sample, regardless of the laser beam diameter, scanning speed, and beam repetition width, if the sample surface temperature is 550°C or higher, the scanning μ- Observation of RHEED images confirmed that single crystallization had occurred. Similarly to Example 1, when the substrate surface temperature is 650°C or higher, when the depth distribution is measured by Auger electron spectroscopy or secondary ion mass spectrometry, it is found that the insulating film on the substrate surface and the second Ar Dissolution of SL and l was observed at the interface.

(Example B4) Example B1, B2. A sample similar to B3 was prepared. Examples B1, B2. The difference from B3 is the shape of the laser beam and the scanning method.

The above sample was laser heated in the following manner. The laser is a continuous wave Ar laser (oscillation wavelength path 488 nm).
and 514.5 nm). The beam shape on the sample is a flat parallel beam as shown in FIG. 6(a). A circular beam 67 was formed into a parallel beam 71 by an optical system 70 using a cylindrical lens. The shape of the parallel beam is approximately 20μm x 1cm, 504m x 1
cm, 10 [μm] x 1 cm. The scanning direction was unidirectional as shown in FIG. 6(a).

The scanning speed of the laser beam is 0.5, 1, 2°5 per minute.
．． It is 10cm. The substrate surface temperature was measured with a radiation thermometer using PbS, and was approximately 450°C, 550″C, and 600°C.
The temperatures are 650°C and 700°C.

The temperature at the substrate surface depends on the laser beam shape, laser output,
It varied depending on the laser beam scanning speed. The following results show that when the laser beam diameter and laser beam scanning speed are given, the surface temperature is 450'C, 550'C, 600'C,
The laser output was changed to 650°C and 700°C. Laser heating was performed in a hydrogen gas atmosphere at atmospheric pressure.

After heat treatment with laser beam, scanning μ-R1 (EE
The results obtained by D microscope, X-ray diffraction method, and conventional RHEED observation are as shown in Examples B1 and B2. Same as B3 (when the substrate surface temperature was approximately 550° C. or higher, the second Ar became single crystallized.

In addition, Examples B1 and B2. Similar to B3, when the substrate surface temperature is 650°C or higher, when the depth distribution is measured by Auger electron spectroscopy or secondary ion mass spectrometry, it is found that Si and Elution of Ar2 was observed.

(Example B5) Example B1, B2. In B3, the sample cross-sectional structure is shown in Figure 1 (
As shown in a), the second l was formed over the entire surface of the sample. In this example, Examples B1, B2. In B3, an insulating film 5 is formed on the second Al as shown in FIG. 1(b), and Examples B1 and B2. Laser heating treatment was performed in the same manner as in B3. SiO□ (hereinafter abbreviated as CVD SiO□) formed as an insulating film on the second Aff by normal pressure CVD, a boron-doped oxide film (hereinafter abbreviated as BSG) formed by normal pressure CVD,
Phosphorus-doped oxide film C formed by normal pressure CVD method
(hereinafter abbreviated as PSG), boron and phosphorous doped oxide film formed by atmospheric pressure CVD method (hereinafter abbreviated as BPSG)
, a nitride film (hereinafter P-
A nitride film (hereinafter abbreviated as ECR-5iN) formed using an ECR apparatus was used. Below is the second
The insulating film on l is a second insulating film. The thickness of the second insulating film is 1000, 2000, 5000, 1
It was set as μm. The laser heating conditions are the same as in Examples 1 and 2.3. After laser heating, the second insulating film was removed by etching to form Examples B1 and B2. Similar to B3, scanning μ-
Electron diffraction pattern, scanning μmRH with RHEED microscope
An EED image was observed. The results obtained are as follows: Examples Bl, B
2. Similar to B3, when the substrate temperature was 550° C. or higher, the second Al became single crystallized. In addition, Examples B1 and B2. Similar to B3, when the substrate surface temperature is 650°C or higher, when the depth distribution is measured by Auger electron spectroscopy or secondary ion mass spectrometry, Si is observed at the interface between the insulating film on the substrate surface and the second l. And dissolution of AI was observed.

(Example B6) In Example B4, the cross-sectional structure of the sample was such that the second Al was formed entirely on the sample surface, as shown in FIG. 1(a). In this example, in Example B4, the first AI is placed on top of the second AI.
As shown in Figure (b), an insulating film was formed and heat treatment using a laser was performed in the same manner as in Example B4. As an insulating film on the second i, CVD SiO□, BSG,
PSG, BPSG, P-SiN, and ECRSiN were used. Hereinafter, the insulating film on the second Al will be referred to as a second insulating film. The thickness of the second insulating film is 1000.

2,000 people, 5,000 people, and 1 μm. The laser heating conditions are the same as in Example B4. After laser heating, the second insulating film was removed by etching, and an electron beam diffraction pattern and a scanning μm RHEED image were observed using a scanning μm RHEED microscope, as in Example B4. As in Example 4, the obtained results showed that the second AI was single crystallized when the substrate temperature was 550'C or higher. Similarly to Example 4, when the substrate surface temperature is 650°C or higher, when the depth distribution is measured by Auger electron spectroscopy or secondary ion mass spectrometry, it is found that the insulating film on the substrate surface and the second AI Si at the interface
And the melting of Al was observed.

(Example B7) Example B1, B2. B3. In B4, S in Fig. 1(a)
The insulating film formed on the i-substrate is made of SiO by thermal oxidation.
It was 2. In this example, CVD Sin□ film, BSG, PSG, BPSG are used as insulating films on the 31 substrates.
, P-3iN, T-SiN, LP-3iN.

ECR-3iN was used. The thickness of these insulating films is 10
00 people, 2500 people, 5000 people, 7500 people,
There are 5 types of 10,000 people.

The thicknesses of the first Al film and the second Al film, and the laser heating conditions were as in Examples B1 and B2. B3. It was similar to B4.

Examples B1, B2. B3. Similar to B4, the second AI became a single crystal when the substrate temperature was 550° C. or higher. Further, Examples B1, B2. B3. Similar to B4, when the substrate surface temperature is 65[]'C or higher, Auger electron spectroscopy,
Alternatively, when the depth distribution was measured by secondary ion mass spectrometry, dissolution of Si and i was observed at the interface between the insulating film on the substrate surface and the second AI.

(Example B8) In Example B7, the cross-sectional structure of the sample was as shown in FIG. 1(a), and the second Al was formed entirely on the sample surface. In this example, the first AI is placed on the second AI in Example B7.
As shown in Figure (b), an insulating film was formed and heat treatment using a laser was performed in the same manner as in Example B7. Second A
[CVD 5102 film as the insulating film on the BSG,
PSG, BPSG, P-5iN, T-SiN,
LP-3iNECR-5iN was used. These insulation 1
The thickness of the mo is 1. OO0 people, 2500 people, 500 people
There are five types: 0 people, 7500 people, and 10000 people.

The thicknesses of the first AI film and the second II film and the laser heating conditions were as in Examples B1 and B2. B3. It was similar to B4. Similar to Example B7, when the substrate temperature is 550°C or higher, the second A
n was single crystallized. Similarly to Example B7, when the substrate surface temperature is 650°C or higher, when the depth distribution is measured by Auger electron spectroscopy or secondary ion mass spectrometry, it is found that the insulating film on the substrate surface and the second Ar2 S at the interface
Elution of j and Al1 was observed.

(Example B9) The second i single crystallized region by laser heating was measured.

A schematic diagram of the sample shape is shown in FIG. 5(a). The cross-sectional structure is
This is the same as in FIG. 1(a). Lines with a width LIO are formed on the insulating film on the Si substrate. The line width LIO is 0.5 μm, 1 gm, and 2 μm.

There are six types: 5 um, 10 um, and 20 um. Si
The (100) and (111) plane orientations of the wafer were used. As the insulating film, SiO□ was used by thermal oxidation. 5i
There are five types of Oz film thickness: 1,000, 2,500, 5,000, 7,500, and 10,000. i deposited on the entire surface of the sea urchin (second Al1.4 in Figure 1(a) or second Al1.4 in Figure 5(a))
The thickness of 3) is 1000 and 2500 people.

There are five types: 5,000 people, 7,500 people, and 10,000 people. 2×5×8×6=480 types of samples were prepared by combining four conditions: the plane orientation of the Si substrate, the 5iO7 thickness, the first i width Lllll, and the second If thickness.

The crystallinity of the second Ar can be determined by X-ray diffraction method, electron beam diffraction pattern observation using a conventional RHEED device, and scanning μm RHEED method.
Microscopic electron diffraction pattern and scanning μmRHE
Observation of the ED image revealed that, as in Example 1, it was polycrystalline, consisting of crystal grains of several to 104+ m.

A continuous wave Ar laser (oscillation wavelength path: 488 nm, 514.5 nm, maximum oscillation output: 20 W) was used as a heating laser. Beam diameter on the sample is approximately 20 μm, 30 μm
They are 70 μm and 100 μm. The scanning direction is shown in Figure 5 (
As shown in a), scanning was performed repeatedly in one direction.

The repetition width of the beam scan was set to be approximately the same size as the beam system. The scanning speed of the laser beam is 0.5 paths per minute,
1.2.5. locm. The substrate surface temperature is Pb
Measured with a radiation thermometer using S, approximately 450°C, 550°
C, 500°C, 650°C, and 700°C. The temperature at the substrate surface varied depending on the laser beam diameter, laser output, and laser beam scanning speed. The following results show that when the laser beam diameter, laser beam scanning speed, and scanning interval are given,
The surface temperature is 450°C, 550°C, 500°C, 650°C.
The laser output was changed so that the temperature was 700°C.

Laser heating was performed in a hydrogen gas atmosphere at atmospheric pressure.

After laser heat treatment, the electron beam diffraction pattern and scanning uRHEED image were observed using a scanning μ-RHEED microscope.
Similarly, a spot pattern with stronger intensity than before the heat treatment was observed (FIG. 14(b)). 111 diffraction spots, 2
The scanning μm RHEED images measured using 02 diffraction spots were similar to FIGS. 17(b) and (c). Here, the first Ar direction (line direction) is X in FIG. 17(a).
parallel to the direction. Further, the scanning direction of the laser is parallel to the X direction. By measuring L8 in FIG. 17(C), the length of the single crystal region can be determined. In FIG. 17(c), 1.8 is shown as if it were approximately 10 to 20 μm, but when the substrate temperature was 550° C. or higher, L8 was approximately 1 cm. That is, the first A which is a single crystal
The second Ar on SiO2 was single-crystalized over a length of 1 cm using l1 as a nucleus. In addition, Examples B1 and B2. B3
．． Similar to B4, when the depth distribution is measured by Auger electron spectroscopy or secondary ion mass spectrometry when the substrate surface temperature is 650°C or higher, it is found that the insulating film on the substrate surface and the second A
Dissolution of Si and A was observed at the interface of [.

(Example B10) A sample was manufactured in the same manner as in Example B9, and heat treated with a laser.

The difference from Example B9 is the sample cross-sectional structure.

In Example B9, the sample cross-sectional structure was as shown in FIG. 1(a) or FIG. 5(a), and the second Ar layer was formed entirely on the sample surface. In this example, the first l is placed on top of the second l.
An insulating film was formed as shown in FIG. 5(b) or FIG. 5(b), and heat treatment using a laser was performed in the same manner as in Example B9. CVD as an insulating film on the second An
5i02. PSG, BSG, BPSG, P-SiN,
ECR-SiN was used. Hereinafter, the insulating film on Ar of cylinder 2 will be referred to as a second insulating film. The thickness of the second insulating film is 10
00 people, 2000 people, 5[)00 people, and 1 μm.

The laser heating conditions are as in Examples B1 and B2. It is the same as B3. After laser heating, the second insulating film was removed by etching, and the electron beam diffraction pattern and scanning μm RHEED image were observed using a scanning μmR1 (EED microscope) as in Example B9. When the temperature was 550° C. or higher, the second 8 ρ became a single crystal. Similar to Example B9, the single crystallized region was observed by scanning μ-RHEED images, as shown in FIGS. 17(b) and (c).
It was the same. L8 was approximately 1 cm. Example 9
Similarly, when the substrate surface temperature is 650°C or higher, when the depth distribution is measured by Auger electron spectroscopy or secondary ion mass spectrometry, it is found that 31 and 31 at the interface between the insulating film on the substrate surface and the second l A! ! , melting was observed under pressure.

(Example Bll) The single crystallized region of the second Aff by laser heating was measured. A schematic diagram of the sample shape is shown in FIG. 6(a). The cross-sectional structure is the same as that in FIG. 1(a). The insulating film on the Si substrate has a width. lines are formed. The sample shape is similar to Example B9. The second crystallinity of l was determined by X-ray diffraction method, electron beam diffraction pattern observation using a conventional RHEED device, electron beam diffraction pattern observation using a scanning μmRHEED microscope, and scanning μRHEED image observation, as in Example 9.
It was polycrystalline with crystal grains of several to 10 μm.

The above sample was laser heated in the following manner. The laser is a continuous wave Ar laser (oscillation wavelength path 488 nm).
and 514.5 nm). The beam shape on the sample is a flat parallel beam as shown in FIG. 6(a). The circular beam was formed into a parallel beam by an optical system 70 using a cylindrical lens. The shape of the parallel beam is approximately 2
0μm×1cm50um×1cm, 100μm
X1cm. The scanning direction was unidirectional as shown in FIG. 6(a).

The laser beam scanning speed was 0.5, 1, 2°5.
It is 10cm. The substrate surface temperature was measured with a radiation thermometer using PbS, and was approximately 450°C, 550°C, 600°C,
650'C, 700°C.

The temperature at the substrate surface depends on the laser beam shape, laser output,
It varied depending on the laser beam scanning speed. The following results show that when the laser beam diameter and laser beam scanning speed are given, the surface temperature is 450℃, 550℃, 600℃, 6
The laser output was changed to 50°C and 700'C. Laser heating was performed in a hydrogen gas atmosphere at atmospheric pressure.

After laser heat treatment, the electron diffraction pattern and scanning μ-RHEED were measured using a scanning μ-RHEED microscope.
When the image was observed, the electron beam diffraction pattern was that of Example B.
Similar to 9, a spot pattern with stronger intensity than before the heat treatment was observed (FIG. 14(b)).

Scanning measured using 111 diffraction spots and 202 diffraction spots! -RHEED images were similar to FIGS. 17(b) and (C). Here, the first Ar direction (line direction) is parallel to the X direction in FIG. 17(a). Further, the scanning direction of the laser is parallel to the X direction. L6 in Figure 17(c)
By measuring , the length of the single crystallized region can be determined. In Figure 17(c), L8 is as if it were 10.
Although it is shown as about ~20 μm, the substrate temperature is 550 μm.
When the temperature was above °C, L8 was approximately 1 cm.

That is, by nucleating the first Aj2 which is a single crystal, 510
The second Ar on 2 was single crystallized over a length of 1 cm. Moreover, Examples B1 and B2. B3. Similar to B4, when the substrate surface temperature is 650°C or higher, when the depth distribution is measured by Auger electron spectroscopy or secondary ion mass spectrometry, it is found that Si and Dissolution of i was observed.

(Example B12) A sample was manufactured in the same manner as in Example B11, and heat treated with a laser. The difference from Example Bll is the cross-sectional structure of the sample. In Example Bll, the cross-sectional structure of the sample was as shown in FIG. 1(a) or FIG. 5(a), and the second l was formed on the entire surface of the sample. In this example,
An insulating film was formed on the second A[ as shown in FIG. 1 (b) or FIG. . Second
CVD SiO, PSG is used as the insulating film on Aj2 of
, BSG, BPSG, P-3iN.

ECR-3iN was used. Hereinafter, the insulating film on Al of cylinder 2 will be referred to as a second insulating film. The thickness of the second insulating film is 100
0 people, 2000 people, 5000 people, and 1 μm. After laser heating, the second insulating film is removed by etching,
As in Example Bll, an electron beam diffraction pattern and a scanning μ-RHEED image were observed using a scanning μm RHEED microscope. The obtained results show that the substrate temperature is 550°C, similar to Example Bll.
When the temperature was above °C, the second l became single crystallized. Example Bl
When the single crystallized region similar to 1 was observed using a scanning μm RHEED image, the results were similar to those shown in FIGS. 17(b) and 17(c). L8 was approximately 1 cm.

Similar to Example Bll, when the substrate surface temperature is 650°C or higher, when the depth distribution is measured by Auger electron spectroscopy or secondary ion mass spectrometry, it is found that at the interface between the insulating film on the substrate surface and the second Aj2. Dissolution of Si and Aff was observed.

(Example B13) Example B9. Laser heat treatment was performed using the same method and procedure as BIO. Example B9. The difference from B10 is the sample shape. The shape of the sample is shown in FIG. 7(a). Example BI
In O, the insulating film on the second Af2 (second insulating film) was uniformly formed on the sample surface, but in this example, the insulating film on the second Af2 (second insulating film)
As shown in Figure (a), it was formed on a stripe in a direction substantially perpendicular to the first l direction (line direction). As the second insulating film, CVD5in, PSG, BSG, BP
SG, P-SiN, and ECR-5iN were used.

The thickness of the second insulating film is 1000 and 2000.

5000 people, 1 μm. The stripe dimensions of the second insulating film are L12, 1.2.5.10tim, L'
Sixteen types of stripes were formed, each consisting of four combinations of s of 1, 2, and 5.10 μm. The laser heating conditions were as in Examples B1 and B2. It is the same as B3. After laser heating, the second insulating film was removed by etching to form Example B.
Similarly to 9, an electron beam diffraction pattern and a scanning μm RHEED image were observed using a scanning μ-RHEED microscope.

The obtained results were similar to Example B9 when the substrate temperature was 550°C.
When the temperature was above °C, the second Aj2 became a single crystal. Example B
When the single crystallized region was observed using a scanning μ-RHEED image as in Example 9, the results were similar to those shown in FIGS. 17(b) and 17(c). L8 was approximately 1 cm. Similar to Example 9,
When the substrate surface temperature is 650℃ or higher, Auger electron spectroscopy,
Alternatively, when the depth distribution was measured by secondary ion mass spectrometry, dissolution of Si and Al was observed at the interface between the insulating film on the substrate surface and the second Al.

(Example B14) A sample similar to that of Example B13 was prepared and subjected to laser heat treatment. The difference from Example B14 is the laser scanning method. The laser scanning method is shown in Figure 10(b).
A parallel beam as shown in Figure 1 was used. The laser includes a continuous wave Ar laser (oscillation wavelength path 488, 5 nm, and 514 nm).
5 nm) was used. The beam shape on the sample is shown in Figure 7 (
It is a flat parallel beam as shown in b). The circular beam was formed into a parallel beam by an optical system 70 using a cylindrical lens. The shape of the parallel beam is approximately 20gm
1 am, 50 μm Xlam, 100 gm
X 1cm. The scanning direction was unidirectional as shown in FIG. 7(b).

The laser beam scanning speed was 0.5, 1, 2°5.
It is 10cm. The substrate surface temperature was measured with a radiation thermometer using PbS, and was approximately 450°C, 550°C, and 600°C6.
50°C and 700°C. The temperature at the substrate surface varied depending on the laser beam shape, laser output, and laser beam scanning speed. The following results show that when the laser beam diameter and laser beam scanning speed are given, the surface temperature is
℃, 550°C, 600°C, 650°C, and 700°C. Laser heating was performed in a hydrogen gas atmosphere at atmospheric pressure.

The obtained results were similar to Example B13 when the substrate temperature was 55.
When the temperature was 0°C or higher, the second Al was single crystallized.

Scanning μ-RHE of the single crystallized region as in Example B13
When observed by ED image, Fig. 17(b) and (
It was the same as c). L8 was approximately 1 cm. As in Example 13, when the depth distribution was measured by Auger electron spectroscopy or secondary ion mass spectrometry when the substrate surface temperature was 650°C or higher, it was found that the insulating film on the substrate surface and the second A [
Dissolution of Si and Al was observed at the interface.

(Example B15) Example B9. B10. B11. B12. B13. B14
For example, the insulating film formed on the Si substrate in FIGS. 5(a) and (b), FIGS. 6(a) and (b), and FIG. 7(a) and (b) is formed by thermal oxidation. It was 5 iOz. In this example, CVD was used as the insulating film on the Si substrate.
5in2 membrane, BSG.

PSG, BPSG, P-5iN, T-3iN,
LP-5iN and ECR-3iN were used. The thickness of these insulating films is 1000, 2500, 5000,
There are five types: 7,500 people and 10,000 people. 1st A
The thicknesses of the E film and the second AE2 film are as shown in Example Bl, B
2. B3. It was similar to B4.

Example B9. B10. B11. B12. B13. B14
Similarly, when the substrate temperature was 550°C or higher, the second l became a single crystal.

Also, Example B9. B10. B11. B12. B13.
Similar to B14, when the substrate surface temperature is 650°C or higher, when the depth distribution is measured by Auger electron spectroscopy or secondary ion mass spectrometry, it is found that Si and Dissolution of 8β was observed.

(Example B16) In Example B1-815, the first, +1 and second A
Both l2 are pure A by LP-CVD method using DMA) l (dimethylaluminum hydride) and hydrogen.
l was used. In this embodiment, instead of pure i, 1-3A
l was used. AE1-3Al was deposited in LP-CVD using DMAH and hydrogen with addition of 5i2Ha.

The Si content in the first AE-3i and second Al2-Si films is 0.2.0.5.1.0%.

In Examples B1 to B15, 11 was replaced with AE-3i, and the same heat treatment as in Examples B1 to B15 was performed.

The results obtained were similar to Examples 81-B15.

(Example B17) In Examples B1 to B15, the first Al2 and the second
Both AE2 are LP-CV using DMAH and hydrogen.
It was formed using D. In order for the second l to become single crystallized by the heat treatment, the first AE needs to be a single crystal. In the LP-CVD method, the first AE and the second Al
It has the advantage of being able to deposit continuously in the same device, but the second
If Al2 is polycrystalline or amorphous, it does not need to be an i-film formed by CVD.

In this example, in Examples B1 to B15, only the second part 8 was formed by sputtering. The second AE is an X-ray diffraction method,
Measurement of the electron beam diffraction pattern using a conventional RHEED device, and observation of the electron beam diffraction pattern and scanning μm RHEED image using a scanning μm RHEED microscope revealed that the deposited state was polycrystalline with a grain size of about 1 μm or less.

When the heat treatment was performed under the same conditions as in Examples B1 to B15, the obtained results showed that, similar to Examples B1 to B15, when the substrate temperature was 550° C. or higher, the second 8ρ became a single crystal. However, the single crystallized region of L8 measured by the same procedure as Examples B9 to B14 was
It was approximately 0.8 cm, shorter than cm.

Also, as in Example B1-815, the substrate surface temperature was 65
When the depth distribution is measured using Auger electron spectroscopy or secondary ion mass spectrometry at temperatures above 0°C, Si and AE are observed at the interface between the insulating film on the substrate surface and the second AE.
Dissolution was observed.

(Example 818) With the same sample shape and heating conditions as Example B1-815, the first AE was an LP using DMAH, hydrogen, and 5iJ6.
- Al2-Si by CVD method, second l is DM
A) Kneading ρ by the LP-CVD method using l and hydrogen was used.

The Si content in the first AE-5i is 0.2.0.5°1.0%.

The results obtained were similar to Examples B1 to B15.

(Example B19) With the same sample shape and heating conditions as Examples B1 to B15, the first Aff was subjected to the LP-CVD method using DMAH, hydrogen, and 512H6: J:6Aj2-3i, and the second Al:
used Al2-3Al produced by sputtering. The Si content in the first Al2-3l is 0.2.0.5.1.
It is 0%.

The results obtained were similar to Examples 81-B15.

However, L8 measured by the same procedure as Examples 89 to B14
The single-crystalline region was shorter (approximately 0.8 cm) than the 1 cm in the second case in which CVD Al was used for l.

(Example B20) In Examples B1 to B19, the sample was heated by irradiating the sample surface with a laser beam. The difference from Examples 1 to 19 was that in heating the sample, heating was performed from the back surface of the sample in addition to laser heating from the front surface. To heat the sample from the back surface, a table (not shown) on which the sample was placed was heated by resistance. The temperature of the back surface of the sample was approximately 250'C, 300C, and 350C. The laser irradiation conditions are the same as in Example B1-819.

The results obtained were similar to Examples 81-B19.

The single crystallization temperature was 550°C in Examples B1 to B19, but in this example, the temperature of the substrate surface was approximately 500°C.
It was made into a single crystal. The single crystallization temperature was lower than that of Examples B1-B19 because the sample was heated from the back side, and the second Al or second Al2-3i on the front surface promoted the flow of Al atoms with lower irradiation energy. It is thought that this was due to an accident.

(Example C1) Samples in which the first i and the second l were deposited were prepared by the method shown in Examples 1 and 2.3, and heated using a linear heater. The pattern of the first insulating film is shown in FIG.
), (b), and (c) are the checker pattern, pier hole pattern, and line & space pattern. The pattern dimensions ˜ls shown in FIG. 2 are the same as Examples 81-B3. In addition, the plane orientation of the Si substrate, the thickness of the first insulating film, and the thickness of the second A[ were also determined in Example B.
It is the same as 1 to B3.

After depositing the first Aff and the second Aj2, evaluation using X-ray diffraction revealed that the 5i02 film thickness, checker size,
Regardless of the film thickness of the second 1, all samples are 1 (111)
Only a peak was observed. Also, the electron beam diameter is 1
When the electron beam diffraction pattern was observed using a conventional RHEED apparatus at a wavelength of 00 prn to 1 mm, a ring-shaped pattern as shown in FIG. 14(a) was observed in each sample. Therefore, it was deposited on the entire surface. It was confirmed that l was a polycrystal with (111) orientation. Furthermore, scanning μmR
When the sample was loaded into a HEED microscope and the electron beam diffraction pattern was observed using an electron beam focused down to 0.1 μm, a spot pattern as shown in Figure 14(b) was observed, although the intensity was weak. It was done. Using the intensity of the diffraction spot on the spot-like diffraction pattern, scan μmR1 (as shown in Figure 15(a), when the EED image is not observed, it is several to 10 μm.
It was polycrystalline, consisting of crystal grains.

The above sample was heated using a linear heater in the following manner.

FIG. 8 shows a heating method using a linear heater. The heating support table 81 is placed on the heating substrate support table 81 . The heating support stand 81 is made of carbon. A linear heater 83 is placed on the heating base 82 . The linear heater 83 is also made of carbon and is energized by a power source 84. Heating support stand 8
1 is also heated by a heater (not shown) attached to the back of the heating support. Moreover, the linear heater 83 has 8
Move in direction 5. Heating was performed under hydrogen atmosphere and atmospheric pressure.

The cotton heater 83 was moved in the direction of the arrow 85. The moving speed is 0.5, 1, 2, 5, and 10 cm per minute. The substrate surface temperature directly below the linear heater 83 was measured with a radiation thermometer using PBS, and was approximately 450°C, 500"C,
They are 600°C, 650°C, and 700°C.

After heat treatment under the above heating conditions, scanning μ-RHEED
In the microscope, electron diffraction patterns and scanning μmRHE
The ED image was observed. Regardless of the surface orientation of the Si wafer, the SiO□ film thickness (first insulating film thickness), the pattern shape/dimensions, and the second l film thickness, for all samples, the substrate surface directly below the linear heater 83 is When the temperature was 550° C. or higher, a spot pattern as shown in FIG. 14(b) was observed in which the electron beam diffraction pattern was stronger than that before heating. The diffraction pattern in FIG. 14(b) shows Al(1
11) This was a diffraction pattern generated when an electron beam was incident on the surface from the [101] direction. Scan μmRH using the intensities of diffraction spot A (C111 diffraction spot) and diffraction spot C (202 diffraction spot) on the diffraction pattern in Figure 14(b).
The results of observing the EED images were similar to those shown in FIGS. 15(b) and (c). In FIGS. 15fb) and 15(c), the shaded areas are regions with strong diffraction spots. In Afflll (second Al film) deposited on the checker pattern, pier hole pattern, and line & space pattern, both diffraction spots A and C were strong, and it was confirmed that the film was single-crystalized by heat treatment. The sample after heat treatment is subjected to conventional R
When observing the electron beam diffraction pattern with a HEED device,
In each sample, a spot pattern indicating a single crystal as shown in FIG. 14(b) was observed.

That is, by heating, A[, which was polycrystalline in the deposited state, became single crystallized. Note that the substrate surface temperature is 650
When the temperature was above ℃, the depth distribution was measured using Auger electron spectroscopy (AES), and it was observed that Al, Si, and O were separated at the interface between SiO□ and the second Ar2.
Heat treatment at 500° C. for 6 hours did not cause single crystallization.

(Example C2) In Example C1, the cross-sectional structure of the sample was as shown in FIG. 1(a), and the second Al was formed entirely on the sample surface. In this example, an insulating film was formed on the second eight ρ as shown in FIG. 1(b), and heat treatment was performed using a linear heater in the same manner as in Example C1. 5iO2 (hereinafter referred to as C
VD 5iOz), boron-doped oxide film formed by atmospheric pressure CVD method (hereinafter abbreviated as BSG), phosphorus-doped oxide film formed by atmospheric pressure CVD method (hereinafter abbreviated as PSG), Boron and phosphorous doped oxide film (hereinafter abbreviated as BPSG),
Nitride film (hereinafter referred to as P-S) formed by plasma CVD method
iN) and a thermal nitride film (hereinafter abbreviated as ECR-5iN) formed by an ECR device. Hereinafter, the insulating film on the second Al will be referred to as a second insulating film. The thickness of the second insulating film is 1000, 2000, and 5000.

It was set to 1 μm. The heating conditions are the same as in Example C1.

After heating, the second insulating film was removed by etching, and an electron beam diffraction pattern and a scanning μmRHEED image were observed using a scanning μmRHEED microscope, as in Example C1. As in Example C1, the obtained results showed that when the substrate temperature was 550° C. or higher, the second Al became single crystallized. In addition, Example C1
Similarly, when the substrate surface temperature is 650°C or higher, when the Auger electron component or the depth distribution by secondary ion mass spectrometry is measured, Si and A4 are observed at the interface between the insulating film on the substrate surface and the second Al. Dissolution was observed.

(Example C3) In Example C1, the first insulating film formed on the Si substrate in FIG. 1(a) was 5iOz by thermal oxidation. In this example, CVD is used as the first insulating film on the Si substrate.
SiO□ film, BSG, PSG, BPSG, P-
SiN, T-3iN, LP-3iN, ECR-S
iN was used. The thickness of these insulating films is 1000 people,
2500 people, 5000 people, 7500 people,
There are 5 types of 10,000 people.

The plane orientation of the Si substrate, the thicknesses of the first Al film and the second Al film, and the heating conditions using the linear heater were the same as in Example C1.

Similar to Example C1, when the substrate temperature is 550°C or higher, the second
8β was single-crystalized. Similarly to Example C1, when the substrate surface temperature is 650°C or higher, when the depth distribution is measured by Auger electron spectroscopy or secondary ion mass spectrometry, it is found that the insulating film on the substrate surface and the second Ar1 Dissolution of Si and A was observed at the interface.

(Example C4) In Example C3, the cross-sectional structure of the sample was as shown in FIG. 1(a), and the second 8β was formed on the entire surface of the sample. In this example, an insulating film was formed on the second Ar1 as shown in FIG. 1(b), and heat treatment was performed using a linear heater in the same manner as in Example C1. CVD SiO□ film, BSG, PSG,
BPSG, P-3iN, LP-3iN, ECR-3iN
was used. The thickness of these insulating films is 1000, 25
00 people.

There are five types: 5,000 people, 7,500 people, and 10,000 people.

The plane orientation of the Si substrate, the thicknesses of the first Al film and the second Al film, and the heating conditions using the linear heater were the same as in Example C3. As in Example C3, when the substrate temperature was 550° C. or higher, the second Ar1 became single crystallized. Similarly to Example C3, when the substrate surface temperature is 650°C or higher, when the depth distribution is measured by Auger electron spectroscopy or secondary ion mass spectrometry, it is found that the insulating film on the substrate surface and the second Al Si and A! at the interface! Dissolution was observed.

(Example C5) The second Al single crystallization region by heating with a linear heater was measured. The sample shape is the same as that shown in FIG. 5(a) in the case of laser heating in Example B9. The cross-sectional structure is the same as that in FIG. 1(a). The insulating film on the Si substrate has a width LIO.
lines are formed. The line width LID is 0.
5 μm, 1 gm, 2 μm, 5 grn.

There are six types: 10 μm and 20 μm. The (100) and (111) plane orientations of the Si wafer were used. As the insulating film, SiO□ was used by thermal oxidation. The SiO□ film thickness is
1000 people.

2500 people, 5000 people, 7500 people, '000
There are 5 types of 0 people. Al deposited on the entire surface of the sea urchin (first
The thickness of the second Al, 4 in the figure or the second 8 ρ63) in Figure 5(a) is 1000, 2500,
5000 people.

7,500 and 10,000 types of plane orientation of the Si substrate: 5tOa thickness, first 8β width. ,
2x5xB made by a combination of 4 conditions with a thickness of 2nd 3℃
x6x=480 types of samples were prepared.

The crystallinity of the second i is determined by X-ray diffraction method, conventional R) (electron beam diffraction pattern observation using EED device, scanning μ-R1 (EED
Microscopic electron diffraction pattern and scanning μ-RHE
From the ED image observation, similar to Examples Bl and CI, several to IO
It was polycrystalline with crystal grains of μm in size.

Heating was performed in the same manner as in Example C1. The moving speed is 0.5, 1. 2. 5.10cm. The substrate surface temperature directly below the linear heater 83 was measured with a radiation thermometer using PBS, and was approximately 450°C, 550°C, and 600°C.
.

The temperatures are 650°C and 700°C. Heating is done in a hydrogen gas atmosphere.

It was carried out at atmospheric pressure.

After the heat treatment, the electron beam diffraction pattern and scanning μmRHEED image were observed using a scanning μmRHEED microscope. As in Example C1, a spot pattern with stronger intensity than before the heat treatment was observed in the electron diffraction pattern ( Figure 14(b)). The scanning μ-R)IEED images measured using 111 diffraction spots and 202 diffraction spots were similar to those in FIGS. 17(b) and (c). Here, the first, l
The direction (line direction) is parallel to the X direction in FIG. 17(a). Further, the scanning direction of the heater is parallel to the X direction. The length of the single crystallized region can be determined by measuring the glue shown in FIG. 17(c). Figure 17(c)
Here, L8 is shown as if it were about 10 to 20 μm, but when the substrate temperature is 550°C or higher, L8 is
I withdrew about 1cm. That is, the first Al which is a single crystal
The second crystal on SiO□ was single-crystalized over a length of 1 cm. Similarly to Example C1, when the substrate surface temperature is 650°C or higher, when the depth distribution is measured by Auger electron spectroscopy or secondary ion mass spectrometry, it is found that the insulating film on the substrate surface and the second Al S at the interface
The dissolution of i and Al was observed.

(Example C6) A sample was produced in the same manner as in Example C5, and heat treated using a linear heater. The difference from Example C5 is the sample cross-sectional structure. In Example C5, the cross-sectional structure of the sample was as shown in FIG. 1(a) or FIG. 5(a), and the second temperature of 3° C. was formed over the entire surface of the sample. In this example, an insulating film is formed on the second 8β as shown in FIG. 1(b) or FIG. Heat treatment was performed. Second Al
Insulating film on top of CVD Sin□, PSG, B
SG, BPSG P-3iN, and ECR-3iN were used. Hereinafter, the insulating film on Al of cylinder 2 will be referred to as a second insulating film.

The thickness of the second insulating film is 1000.

2,000 people, 5,000 people, and 1 μm. The heating conditions using the string heater were the same as in Example C1. After heating, the second insulating film was removed by etching, and as in Example C5, an electron beam diffraction pattern and a scanning μmR) IEED image were observed using a scanning μmR) IEED microscope.

The obtained results are similar to Example C5 when the substrate temperature is 550
℃ or higher, the second Al was single crystallized. Similar to Example C5, scanning μmR similar to FIGS. 17(b) and (c)
A HEED image was obtained, and the single crystallized region L8 was approximately 1 cm.
Met. Similar to Example C5, the substrate surface temperature is 650°.
C or more, when the depth distribution is measured by Auger electron spectroscopy or secondary ion mass spectrometry, it is found that Si and Af are present at the interface between the insulating film on the substrate surface and the second Aj2.
The dissolution of No. 2 was observed.

(Example C7) In Examples C5 and C6, for example, FIGS.
), the insulating film formed on the Si substrate was SiO□ by a thermal oxidation method. In this example, the insulating film on the Si substrate is a CVD SiO2 film, BSG, PSG.
.

BPSG, P-5iN, T-5iN, LP-5i
N, ECR-5iN was used. The thickness of these insulating films is 1000, 2500, and 5000.

There are five types: 7,500 people and 10,000 people. The plane orientation of the Si substrate, the thicknesses of the first 1 film and the second Al2 film, and heating conditions using a linear heater were the same as in Example C1.

As in Examples C5 and C6, when the substrate temperature was 550° C. or higher, the second 8β became a single crystal. Similar to Examples C5 and C6, the same scanning μmRH as in FIGS. 17(b) and (c)
An EED image was obtained, and the single crystallized region L6 was approximately 1 cm. Similar to Examples C5 and CB, the substrate surface temperature was 65
When the depth distribution is measured using Auger electron spectroscopy or secondary ion mass spectrometry at temperatures above 0°C, Si and Al are observed at the interface between the insulating film on the substrate surface and the second 8ρ.
Dissolution was observed.

(Example C8) In Examples 01 to C7, the first Al and the second A! In both cases, pure Al was used by the LP-CVD method using DMAH and hydrogen.

In this example, Al2-3L was used instead of pure Aff. In LP-CVD using DMAH and hydrogen, 5
Al-3Al was deposited by adding i2Hs. 1st A
The Si content in l2-3i and the second Al-Si film is 0.2.0.5.1.0%. Examples 01-C7
The same heat treatment was performed.

The results obtained were similar to Examples C1-C7.

(Example C9) In Examples C1 to C7, both the first Al2 and the second Al were formed using LP-CVD using DMAH and hydrogen. In order for the second Al to become single crystallized by the heat treatment, the first Al needs to be single crystal. L
The P-CVD method has the advantage that the first Al and the second Aff can be deposited successively in the same apparatus, but the second Aff
l2 does not need to be a CVD film as long as it is polycrystalline or amorphous.

In this example, only the second Al was formed by sputtering using the same sample and heat treatment conditions as Examples 01 to C7. Second
When Al was subjected to X-ray diffraction method, electron beam diffraction pattern measurement using a conventional RHEED device, electron beam diffraction pattern and scanning μ-RHEED image observation using a scanning μm RHEED microscope, it was found that in the deposited state, the grain size was approximately 1 μm or less. It was polycrystalline.

When heat treated under the same conditions as Examples C1-C7,
The obtained results showed that the second Al was single crystallized when the substrate temperature was 550° C. or higher, similar to Example C1-07. however,
The single crystallized area of L8 measured using the same procedure as Examples 05 to C7 was 1 cm using CVD Al as the second Al.
and shorter (approximately 0.8 cm).
Similar to C7, when the substrate surface temperature is 650°C or higher, when the depth distribution is measured by Auger electron spectroscopy or secondary ion mass spectrometry, it is found that the insulating film on the substrate surface and the second A
The dissolution of Si and i was observed to be compressed at the interface of l.

(Example Cl0) Using the same sample shape and heating conditions as Examples C1 to C7, the first
Al contains DMAH, hydrogen and S! LP using 2H6
- Al-3i by CVD method, DM
Pure Al obtained by LP-CVD using AH and hydrogen was used.

The Si content in the first Al-Si is 0.2.0.5°1.0%.

The results obtained were similar to Examples C to C7.

(Example C11) Using the same sample shape and heating conditions as Examples C1 to C7, the first
, l is LP using DMAI (and hydrogen and SLH).
-Al2-5i produced by CVD method, and 8β-5Al produced by sputtering method was used for the second (7)i. 1st Aff-
The Si content in 3i is 0.2.0.5.1.0%.

The results obtained were similar to Example Cl-C7. However, the single crystallized region of L8 measured using the same procedure as Examples 05 to C7 was
cm (approximately 0.8 cm).

(Example DI) Samples similar to those shown in Examples 01 to C11 were prepared and heated using a lamp.

FIG. 9 shows a heating method using a lamp.

The heating substrate 92 is placed on the heating substrate support 91 . The heating support stand 91 is made of carbon. In the lamp 93,
A linear Xe lamp was used. The light from the lamp 93 is focused by a reflecting mirror 94 so that it forms a line on the surface of the substrate. The heating support table 91 is also heated by a heater (not shown) attached to the back surface of the heating support table. Further, the heating region 95 was moved on the heating substrate by the movement of the lamp.

Heating was performed in a hydrogen atmosphere at atmospheric pressure.

By moving the base support 91, the heating area is moved in the direction indicated by the arrow 9.
Moved in direction 6. The moving speed is 0.5, 1 road per minute.
．． 2. 5.10cm.

The substrate surface temperature of the heating area 95 was measured with a radiation thermometer using PBS, and was approximately 450°C, 550°C, 600°C, and 65°C.
0"C, 700°C.

When heated using the method shown above, the results obtained were as follows.
It was the same as Example Cl-C11.

(Example El) Samples similar to those shown in Examples 01 to C1l were prepared and heated using high frequency.

A heating method using high frequency heating will be explained with reference to FIG.

The heating substrate 103 is placed on a heating substrate support. 10
1 is a support made of carbon. Also, ]02 is a plate made of quartz. As shown in FIG. 1O, the heating support on which the substrate was placed was heated by a high frequency coil (not shown) provided around the heating support. Since the quartz plate 102 is not heated by high frequency, a portion 104 on the base is heated to the highest temperature.

By moving the wafer in the direction indicated by arrow 105, region 104 heated to a high temperature also moves over the wafer. Heating was performed under hydrogen atmosphere and atmospheric pressure. The moving speed is 0.5, 1, 2, 5°10 cm per minute. The substrate surface temperature of the heating region 104 was measured with a radiation thermometer using PbS, and was approximately 450°C, 1550°C, 600°C, 6
50°C and 700°C.

When heated using the method shown above, the results obtained were as follows.
Example CI- (1:11).

(Example Fl) Samples similar to those shown in Examples C1 to C1l were prepared and heated using an electron beam.

FIG. 11 shows a heating method using an electron beam.

The electron beam 113 from the filament 112 is directed to a focusing coil and a scanning coil 115 . The light is focused linearly on the heating substrate 114 by the deflection plate 115'. On the substrate, III
is heated linearly to a high temperature. The wafer is arrow 11
By moving in the direction indicated by 6, the region 114 heated to a high temperature also moves on the wafer. The heating atmosphere pressure was a vacuum atmosphere of 10-' Torr or less.

The moving speed of the base is 0.5.1, 2, 5° 10c per minute.
It is m. The substrate surface temperature in the heating region was measured with a radiation thermometer using PBS, and was approximately 450°C and 550°C.

They are 600°C, 650°C, and 700°C.

When heated using the method shown above, the results obtained were as follows.
It was the same as Examples 01-C11.

[Effects of the Invention] As explained above, according to the present invention, single crystal Al can be formed on the surface of a base made of any base material.

Further, it is possible to form an l-wiring having favorable characteristics as a wiring material for a semiconductor device, such as surface properties, anti-microbial properties, and interfacial properties with underlying Si.

[Brief explanation of drawings]

Fig. 1 is a schematic cross-sectional view for explaining the single crystallization method according to the present invention and the wiring formation method using the same, and Fig. 2 (a), (b), and (c) are applicable to the present invention. FIG. 3 is a schematic top view for explaining a single crystal i-seed pattern, FIG. 4 is a schematic diagram for explaining a scanning μm RHEED microscope, and FIG.
Figures (a) and (b) are schematic diagrams (Fig. 6) for explaining the sample shape and laser beam irradiation method applicable to the present invention.
a) and (b) are schematic diagrams for explaining the sample shape applicable to the present invention and the laser beam irradiation method. A schematic diagram for explaining the laser beam irradiation method. FIG. 8 is a schematic diagram for explaining the heating method using a linear heater. FIG. 9 is a schematic diagram for explaining the heating method using a lamp. The figure is a schematic diagram for explaining a heating method using high-frequency heating method. Figure 11 is a schematic diagram for explaining a heating method using an electron beam. Figure 12 is a scanning μm R) Principle of IEED. FIG. 13 is a schematic diagram for explaining the principle of scanning μ-RHEED microscopy. FIG. 14 is a diagram showing electron diffraction patterns.
Figure 7 shows an example of a scanning μm RHEED image showing the grain boundaries of the Al film deposited on the entire surface of the sample. ), 1... Si substrate, 2... First insulating film, 3... First Al, 4... Second Aj2. 5... Second insulating film, 6... Third l (selective growth Al), 7... Fourth Al, 8... Third insulating film, 11... Insulator part, DESCRIPTION OF SYMBOLS 12... Opening part, 20... Electron gun, 21... Electron beam, 22... Diffraction electron beam, 23... Fluorescent screen, 24, 24', 24... Optical fibers . 25, 25', 25''...Photomultiplier tube, 26 2
6', 26''...Diffraction spot intensity converted to electric signal, 27...Scanning signal, 28...CRT. 29...Secondary electron signal, 30...Secondary electron detector, 31... Sample, 34... Vacuum chamber 35... Exhaust device, 61... Si substrate, 62... First l, 63... Second 8ρ, 64... No. 1 insulating film, 65...2nd insulating film (second insulating film on l), 66
...Insulating film on the stripe on the second Aj2, 67...
・Laser beam, 68... Repeated laser scanning direction, 69... Laser scanning direction, 70... Optical system for making the laser beam parallel, 71... Parallel laser beam, 81... Base support Stand, 82... Heating base, 83... Linear heater 84... Power source, 85... Linear heater scanning direction, 91... Base support, 92... Heating base, 93... - Linear lamp, 94... Reflection mirror 95... Heating area, 96... Light scanning direction, 101... Base support made of carbon, 102... Base support made of quartz, 103... - Heating substrate, 104... Heating region, 105... Heating substrate movement direction, 111... Heating substrate, 112... Filament, 113... Electron beam, 114... Linearized electron beam, 115, 115
'...Focusing lens and deflection lens, 116...
Heating substrate moving direction, 200...Base, 201...Quartz base support, 202...Quartz tube, 203...Lamp, 204...Reflector plate. Figure 1 Figure 6 (G) Figure 6 (b) Figure 7 (b) Figure 8 Figure 9 Figure 12 Figure 4: ＼ ・ @ Figure 14-47F) - H → Pito(ri)

Claims (1)

[Claims] 1) A non-single-crystal metal film made of Al or an Al alloy containing Al as a main component is formed at least in part in contact with a single-crystal metal film made of Al or an Al alloy containing Al as a main component. A method for forming a metal thin film, comprising: a step of heating the non-single crystal metal film to make at least a portion of the non-single crystal metal film into a single crystal. 2) forming an insulating film on the main surface of a semiconductor substrate; providing an opening in the insulating film to expose the surface of the semiconductor; and depositing Al or Al containing Al as a main component in the opening. a step of depositing a single crystal made of a first metal made of an alloy; and a step of depositing a second metal made of Al or an Al alloy containing Al as a main component on the single crystal made of the first metal and on the insulating film. A semiconductor characterized by comprising a step of forming a thin film, and a step of heating the thin film of the second metal using a single crystal of the first metal as a seed crystal to make at least a part of it into a single crystal. Metal thin film formation method using equipment. 3) As the single crystal made of the first metal, an Al single crystal is selectively deposited in the opening by a CVD method using dimethylaminium hydride gas and hydrogen gas. Metal thin film formation method. 4) The metal thin film forming method according to claim 2 or 3, wherein the heating is performed after further forming a second insulating film on the second metal thin film. 5) The metal thin film forming method according to any one of claims 2 to 4, characterized in that the second metal thin film is heated to 550° C. or higher. 6) The metal thin film forming method according to claim 5, wherein the second metal thin film is heated by a resistance heating method. 7) The metal thin film forming method according to claim 5, wherein the second metal thin film is heated by a radiation heating method. 8) The metal thin film forming method according to claim 5, wherein the second metal thin film is heated by a laser beam heating method. 9) The metal thin film forming method according to claim 5, wherein the second metal thin film is heated by an electron beam heating method. 10) The metal thin film forming method according to claim 5, wherein the second metal thin film is heated by an induction heating method.