JPH07183103A - Heating resistor, inkjet head substrate, inkjet head, and method for manufacturing the same - Google Patents

Abstract

(57) [Summary] [Purpose] High durability and high definition and high speed recording are possible. [Structure] T having a (101) plane orientation by X-ray diffraction
Provided are a heating resistor having a ₂ N and (110) oriented TaN, and an inkjet head substrate and an inkjet head having a layer 103 of the heating resistor. Further, the heating resistor is formed by sputtering or reactive sputtering.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heating resistor, an ink jet head substrate, an ink jet head and a method for manufacturing the same.

[0002]

2. Description of the Related Art An ink jet recording method (liquid jet recording method) is put to practical use in that it can be reduced in noise and size, is suitable for high speed and high definition recording, and can be applied to so-called plain paper. ing.

Among them, JP-A-54-59936,
JP-A-54-59139, JP-A-55-2728
The method (bubble jet method) described in Japanese Patent Laid-Open No. 1 and Japanese Patent Laid-Open No. 55-27282, which uses thermal energy to generate bubbles and ejects ink to perform recording (bubble jet method), has further advantages. It is possible and can be achieved at a higher level, and is attracting attention.

In the ink jet head of such a system, at least the surface has an insulating substrate and a heating resistance layer,
It usually has a heating resistance element having at least a pair of electrodes electrically connected to the heating resistance layer. In addition, the heating resistor element is provided with a protective layer to protect it from oxidation by ink and other protection.
It also prevents short circuits between electrodes.

The heating resistance element is electrically connected to a drive circuit having a functional element provided separately by a flexible cable or wire bonding.

By the way, with respect to the head configuration described above,
In order to further simplify the structure, reduce the defect rate in the manufacturing process, and make the characteristics of each element uniform, JP-A-57-72 is known.
In Japanese Patent No. 867, it is proposed to provide a heating resistance element and a functional element on the same substrate.

Such an ink jet head substrate 2
An example of No. 01 will be described with reference to FIGS. 14 and 15.

The ink jet head shown in FIG. 14 corresponds to an electric / thermal converting element array portion 202 and an electric / thermal converting element which are constituted by arranging a plurality of electric / thermal converting elements (heating resistance elements) in an array. A predetermined shape in order to form a common liquid chamber and a liquid passage (flow passage) for supplying liquid with a device attachment member 201 having a driving circuit portion 203 formed of functional elements provided on the surface portion. Basically, the groove cover member 204 is provided with a predetermined number of grooves having the following dimensions.

The groove cover member 204 has a groove 106 so that each groove 206 covers each of the electric / thermal conversion elements 105 which are regularly arranged at a predetermined interval and a predetermined size. Groove cover member 2 at a pitch such as the arrangement pitch of 205
04, each groove 106 is connected to a common liquid chamber groove 207 provided in the rear of the groove lid member 204 and in a relationship perpendicular to the direction in which each groove 106 is provided.
The groove cover member 204 is provided on each element array member 202 of each groove 20.
6 and corresponding electric / heat conversion elements 205 are joined so as to face each other, and a plurality of flow paths having a heat action chamber part in a part thereof and liquids for filling these flow paths with liquid A common liquid chamber for supplying each of the flow paths to each flow path is formed.

A supply pipe 208 for supplying the liquid to the common liquid chamber from a liquid storage tank (not shown) provided outside is attached to the rear of the common liquid chamber groove 207.

The electrothermal conversion element 205 is generated between a common electrode 209 common to each element and an electrode 211 connected to the collector section of a transistor 210 as a functional element forming the drive circuit section 203. The heat generating resistor portion 212 is provided for causing the generated heat to act on the liquid.
Although not shown in the drawings, electrical insulation is provided on the entire surface of the electrothermal conversion element array portion 202 in order to prevent contact between the liquid and the heat generating resistance portion 212 and electrical leakage between the common electrode 209 and the collector electrode 211. A protective layer is provided.

The drive circuit section 203 includes a collector electrode 21.
1, a collector region, a base region, and an emitter region are formed below the base electrode 213 and the emitter electrode 214, respectively. These regions are the semiconductor substrate 2
It is structurally provided inside the surface of 15. Each base electrode 2
Reference numeral 13 is formed continuously with the base common electrode 216 attached to the rear. 217 is each transistor 210
Is an electrode for applying a high voltage to the collector region for electrical isolation, and is common to each transistor.

FIG. 15 schematically shows a sectional structure when the head shown in FIG. 14 is cut along a flow path.

The element attachment member 201 has a structure in which each functional element is structurally provided inside the surface thereof, is composed of a semiconductor substrate 218 and an epitaxial layer 219, and the epitaxial layer 219 has an electric / thermal conversion element 205. Also, a transistor 210 as a functional element is provided internally.

The electricity / heat conversion element 205 includes a heating portion 212 and a common electrode 20 on the surface of the epitaxial 219.
9 and an electrode 211 for connecting to the collector region of the transistor 210, and the heating portion 212 is a heating resistor 2
20 and a protective layer 22 for protecting the heating resistor 220
It is composed of 1 and 1.

The heat generating portion 212 is provided on the heat generating portion 212.
A heat action chamber 222 is formed as a place where the liquid causes a rapid state change including generation of bubbles and contraction of the volume thereof under the action of heat generated. Heat action chamber 222
Respectively communicate with a discharge port 223 through which liquid is ejected to form flying droplets based on the above state change, and a common liquid chamber 224 provided in the rear, and the common liquid chamber 224 has A supply pipe 108 for supplying a liquid to the common liquid chamber 224 from the outside is attached.

Behind each of the electricity-heat conversion elements 205, a corresponding transistor 210 is epitaxially formed.
It is structurally provided inside 9. Transistor 21
0 has a normal transistor structure, and a buried layer 228-1 for reducing the resistance of the collector region 225 is provided at the bottom portion. An ohmic region 228-2 for forming ohmic contact is provided between the electrode 211 and the collector region 225.

Collector region 225, base region 226,
Electrodes 211, 213, 214, and 217 are taken out from the emitter region 227 while being electrically isolated from each other. Electrical insulating layers 229-1 and 229-2 are formed between the emitter electrode 214 and the base electrode 213 and the electrode 217 for electrical isolation in order to form electrical isolation in the overlapping portion. Intervened.

When used as an ink jet head, as shown in FIG. 15, a liquid chamber or liquid path for holding ink is formed on the substrate 201 corresponding to the heat generating portion 212, and ink is ejected. The discharge port of is provided as needed.

As the heat generating resistor forming the heat generating resistance layer 220, one having a small heat capacity, good adhesion to the base and high mechanical strength is preferable, and therefore tantalum nitride, a nickel chromium alloy, Materials such as tantalum silicon dioxide are commonly used.

Among them, tantalum nitride is a preferable material because it has a simple composition, has excellent heat resistance peculiar to refractory metals, and can form a heating resistance layer by a simple manufacturing method.

As a method for producing the heat generating resistance layer using tantalum nitride, for example, a reactive sputtering method using a mixed gas of Ta target, Ar (argon) and N ₂ (nitrogen), or sintering of a predetermined composition is carried out. The sputtering method using the body as a target, a vapor deposition method, a CVD method, and the like can be given.

The composition and physical properties of the tantalum nitride film formed on the substrate by the above method largely depend on the film forming conditions.

Tantalum nitride used as a heating resistor generally has a composition having a molar weight ratio based on N of Ta of 2.0, and has a surface area as shown in FIGS. 7 and 10. A hexagonal Ta ₂ N film showing azimuth (002) and (101) orientation has been considered preferable because it has excellent durability.

[0025]

However, in order to satisfy the recent demands for higher integration, higher reliability, lower cost, high speed, and high quality recording of heads and devices, the above-mentioned heat resistance is required. The body still had room for improvement.

For example, in order to improve the recording quality (image quality), it is necessary to improve the recording density that determines the pixel unit. In other words, the heat-generating resistance elements are made even more dense,
Therefore, it is necessary to arrange them so that they become finer. Specifically, in recent years, a high resolution of at least 400 dpi or more has been required.

Further, in order to perform high speed recording, it is necessary to improve the ink ejection frequency. Therefore, the heat generating resistance element (heat generating resistor) is required to further improve the thermal response and heat resistance and to withstand the heat stress.

In other words, in order to achieve high integration and high speed recording, the specifications of the heating resistor required must be further improved so as to withstand more severe use.

However, in general, the tantalum nitride film obtained by the above-mentioned manufacturing method has a problem that when it is used as a heating resistance element corresponding to such a use situation, the resistance value varies greatly and the wire is easily broken. It is easy to occur.

In particular, in a method of ejecting ink by utilizing thermal energy such as a bubble jet method, a driving pulse width is several μs to + several μs in order to vaporize ink (liquid), condense it, and eliminate bubbles. Since it is necessary to heat the heating resistor at a high temperature of 600 to 900 [deg.] C. and to lower the temperature in a short time in a short time, it may be difficult to say that the resistor has sufficient reliability.

It is an object of the present invention to solve the above problems and provide a heating resistor, an ink jet head substrate and an ink jet head which are capable of high speed recording and high resolution recording and have high durability.

It is another object of the present invention to provide a method for manufacturing a heating resistor that achieves the above object.

[0033]

The heating resistor of the present invention which achieves the above object is a heating resistor having tantalum nitride, wherein the tantalum nitride has a peak with a plane orientation of (101) orientation by X-ray diffraction. Indicating that Ta ₂ N and the plane orientation are (1
10) It has TaN showing a peak of orientation.

In addition, the ink jet head substrate of the present invention that achieves the above object has a substrate, a heating resistor layer (heating resistor layer) formed on the substrate, and a gap between the heating resistor layer. A substrate for an inkjet head having at least an electrothermal conversion element having a pair of electrodes electrically connected thereto, wherein the layer of the heating resistor has a plane orientation of (101) by X-ray diffraction. ) Ta showing a peak of orientation
It is formed of tantalum nitride having a TaN indicating the peak of ₂ N and (110) orientation.

Further, the method for manufacturing a heating resistor of the present invention which achieves the above object is the method for manufacturing a heating resistor having tantalum nitride, wherein the tantalum nitride has a peak of (101) orientation in a plane orientation by X-ray diffraction. Ta ₂ N and (1
10) It has TaN showing a peak of orientation, and the tantalum nitride is formed by a reactive sputtering method or a sputtering method.

Thus, in the present invention, the tantalum nitride film having excellent heat resistance and thermally stable characteristics is used as the heating resistor to prolong the life of the heating portion and to meet more stringent specifications. Can be the body. In addition, more stringent specifications such as high-speed recording property, high-resolution recording property, durability, low cost, and uniform product characteristics are required. It is possible to provide a substrate for an inkjet head and an inkjet head.

[0037]

EXAMPLES The present invention will be described in detail below with reference to the drawings, but the present invention is not limited to the following examples, and can be appropriately modified within the scope of the gist of the present invention.

Example 1 FIG. 1 is a schematic sectional view of an ink jet head substrate manufactured according to the present invention.

In FIG. 1, 2 is a P-type single crystal silicon substrate, 2 is an N-type collector region, 3 is a P-type isolation buried region, 4 is an N-type epitaxial region, 5 is a P-type base region, and 6 is P. Type isolation region, 7 is an N type collector region, 8 is a high concentration P type base region, 9 is a high concentration P type isolation region, 10 is a high concentration N type emitter region, 11 is a high concentration N type collector region, 12 Is a collector
Base common electrode, 13 is an emitter electrode, 14 is an isolation electrode, 101 is a heat storage layer, 102 is an interlayer film, 10
3 is a heating resistance layer, 104 is a wiring electrode, 104 ₁ is an edge portion of the wiring electrode 104 such as aluminum, and 105 is Si.
A first protective layer, such as O ₂ , 106 is a second protective layer, 11
Reference numeral 0 is a heat generating portion, and 120 is an NPN transistor (bipolar transistor).

A substrate 100 as a substrate for an ink jet head includes a heat generating portion 110 corresponding to a heat generating region of an electric / heat converting element (heat generating resistance element) and a bipolar type NPN transistor 120 which is a driving function element and a P type silicon. It is formed on the substrate 1. The heating resistance layer 103 is
The N-type epitaxial region 4, the heat storage layer 101, and the interlayer film 1 which is also provided integrally with the heat storage layer 101 and serves as a heat storage layer.
It is formed on the P-type silicon substrate 1 via 02.
A desired portion of the wiring electrode 104 formed on the heating resistance layer 103 is removed to form a heating area. Edge portions 104 ₁ are formed on the connection end faces of the wiring electrodes, respectively.

The heat storage layer 101 is controlled so that the heat from the heat generating resistance layer 103 of the heat generating portion 110 is transferred to the upper side in the figure for a short time and is easily transferred to the P-type silicon substrate side on the lower side in the figure for a long time. It is a layer for doing. Of course, the interlayer film 102 also has a similar function.

Further, the heat generating portion 110 corresponds to the heat generating resistance layer 103 in the gap portion of the wiring electrode 104 in the example shown in the figure.

In FIG. 1, an interlayer film 102 is provided to prevent unnecessary contact between the wiring or isolation electrode to the NPN transistor 120 and the heating resistance layer 103 or the wiring electrode 104.

Further, the substrate 1 for the ink jet head
00 is entirely covered with a heat storage layer 101 formed of a thermal oxide film or the like, and each electrode 12, 13, 14 is
It is formed of 1 or the like. In addition, each electrode 12, 13, 14
2 is an enlarged side view (electrodes 14, emitters, collectors, bases, etc. are omitted) of FIG. 2 and FIG. 3, the inclined side surface (end portion is 30 degrees or more and 75 degrees or less) with respect to the normal line. )
have.

In the substrate 100 of this embodiment, a collector / base common electrode 12, an emitter electrode 13 and an isolation electrode 14 are formed on a P-type silicon substrate 1 for a recording head having the above-mentioned drive section (functional element). It is covered with a heat storage layer 101, and an atmospheric pressure CVD method is used for the upper layer.
Silicon material Si by PCVD method sputtering method, etc.
Interlayer film 10 made of O, SiO ₂ , SiN, SiON, etc.
2 is formed. Since Al or the like forming each of the electrodes 12, 13, 14 has inclined side surfaces, the step coverage of the interlayer film 102 is very excellent.
No. 02 can be formed thinner than the conventional one within a range in which the heat storage effect is not lost. The interlayer film 102 is partially opened to form a collector / base common electrode 12 and an emitter electrode 13
And Al for electrically connecting to the isolation electrode 14 and for forming an electrical wiring on the interlayer film 102.
The wiring electrodes 104, etc. are installed. That is, the interlayer film 1
After the hole 02 is partially opened, an electric / heat conversion element including a heating resistance layer 103 and a wiring electrode 104 of Al or the like formed by a vapor deposition method or a sputtering method is provided. Of course, the ink jet head is manufactured by providing the base 100 with openings such as liquid paths and ejection openings as shown in FIG.

FIG. 4 is an enlarged sectional view of the electricity / heat converting element, and FIG. 5 is an enlarged plan view of the electricity / heat converting element.

The wiring electrode 104 of Al or the like has an edge portion 104 ₁ and a side surface 104 ₂ which are connection end surfaces inclined by 30 ° or more with respect to the normal line. Further, on the heat generating portion 110 of the electrothermal conversion element shown in FIG. 1, SiO, SiO ₂ , SiN,
Protective film 105 such as SiON and protective film 106 such as Ta
Are provided integrally with the interlayer film 102.

Further, the base 100 is provided with the wiring electrode 10.
The edges 104 ₁ and both side surfaces 104 ₂ (see FIG. 5) of _No. 4 have a linear taper shape, and the edges of the collector / base common electrode 12, the emitter electrode 13 and the isolation electrode 14 and both end surfaces are The shape is also a linear taper, as shown in FIGS. 2 and 3, respectively.

A method for forming the heating resistance layer 103 used for the above-mentioned ink jet head substrate in the case of using the reactive sputtering method will be described.

First, the base film and the contact portion of the heating resistor are etched by tens of liters by Rf sputtering to obtain a clean surface. Then, using a Ta target, Ar and N ₂
The pressure of the mixed gas atmosphere is set to 5 to 10 mTr, and the N ₂ gas partial pressure ratio to the mixed gas is set to ₂₀ to 3
It is set to 0%, preferably 22 to 26%. After setting the substrate temperature to 200 to 300 ° C., DC power of 1.0 to 3.0 kw is applied. These series of film forming processes are performed in a high vacuum without exposing to the atmosphere. By the forming method described above, the tantalum nitride film which is the heat generating resistance layer 103 is deposited.

Here, the N ₂ partial pressure and Ar + N ₂ are shown in FIG.
The specific resistance of the tantalum nitride deposited on the substrate with respect to the ratio with the mixed gas pressure and the film composition ratio measured by EPMA are shown. As the N ₂ partial pressure increases, the ratio of Ta in the film decreases and the specific resistance increases. Characteristic is N ₂ partial pressure 22
The region of up to 26% is a so-called plateau region, which shows a substantially constant value of resistivity, and the film composition ratio is Tax.
N; 1.4 ≦ x ≦ 1.9. The measurement of FIG. 6 shows the composition ratio at a typical position of the wafer, and Table 1 shows the variation of the composition ratio in the wafer at that time, the specific resistance, and the main diffraction peaks of the tantalum nitride film by X-ray diffraction measurement. . The diffraction peak of the tantalum nitride film formed on the substrate by the reactive sputtering method changes with an increase in the N ₂ partial pressure ratio, and the diffraction peaks shown in FIGS.
Shows two patterns. Temporarily, the pattern (I), the pattern (II), and the pattern (III) are set. That is, N
_{At the 2} partial pressure ratio of 20%, typical peaks of hexagonal Ta ₂ N (002) and (101) are shown (pattern (I)), and at the N ₂ partial pressure ratio of 30%, the hexagonal Ta is N.
The representative peaks of N (110) and (101) are shown (pattern (II)). Also, the N ₂ partial pressure ratio is 22 to 26.
% Region, the (101) peak of hexagonal Ta ₂ N and the (110) peak of hexagonal Ta ₂ N were observed (pattern (III)).

Table 3 shows the results of a study on the evaluation of film quality as an ink jet head manufactured by using tantalum nitride heat generating resistors prepared at various N ₂ flow rate ratios.

Here, the breaking voltage ratio in Table 3 means various N
A pulse signal of 7 μs is applied to the ink jet head formed with the _two flow rate ratios, and the threshold voltage Vth for starting ejection is determined. After that, the applied voltage is increased from Vth by 0.02Vth at about ² pulses at 2 KHz until the heater breaks, and the voltage at break is set to Vb. The ratio between the threshold voltage and the breaking voltage Vb is the breaking voltage ratio Kb.
(= Vb / Vth). The higher the value of this breaking voltage Kb, the higher the heat resistance of the heater element. This heat resistance is not only the heat resistance of the heater material, but is several μs in order to instantly vaporize and condense like a liquid jet recording head.
It is necessary to heat and cool in a very short time of up to tens of μs, and in order to vaporize the liquid instantaneously, the liquid interface on the heater element has a normal boiling point (100 ° C. in water) of about Since the temperature required is about 3 times (300 ° C. with water) and the time required for heat transfer is short, it is necessary to heat the heater material at once to 600 to 900 ° C. For that purpose, not only the heat resistance of the heat-resistant protective film of the heater material, but also the stress and adhesion between the materials that make up the entire heater element, as well as the design considering physical and scientific alterations between the materials. Should.

From Table 3, the N ₂ partial pressure ratio is 22 to 26%, the composition ratio TaxN is 1.4 ≦ x ≦ 1.9, and the tantalum nitride film having the X-ray diffraction pattern (II) has a high Kb value of 1.7 to 1. .8
The films with the N ₂ partial pressure ratios of 22% and 30% showed lower values than the tantalum nitride film formed with the N ₂ partial pressure ratio.
Generally, the actual driving and voltage of the inkjet head is 1.2 Vth, where Vth is the lowest voltage at which ink is ejected, and 1.3 or more is a usable level in consideration of variations and the like. However, it can be said that the higher the value of Kb, the higher the heat resistance margin and the higher the reliability.

Next, the resistance change rate in Table 3 is a pulse signal of 7 μs, the applied voltage is 1.2 Vth, the ejection frequency is 3 KHz at the maximum, and the recording head is attached to the printer. Print and print 100
The resistance change rate at the time of recording 0 sheets was obtained.
R ₀ is the initial heater resistance, and ΔR is the resistance change after the test with respect to the initial stage.

Similarly to the breaking voltage, the N ₂ partial pressure ratio 22 in Table 3 is
.About.26%, the film of X-ray diffraction pattern (II) shows a small value of resistance change rate, and at the time of 1000 sheets, -1.5 to +1.
The resistance value is 0, which is almost the same as the initial resistance value.

N ₂ partial pressure ratio 30%, X-ray diffraction pattern (I
In the case of the film of II), the rate of resistance change reaches + 10%. When the resistance of the heater material is increased, the applied voltage is constant, so the energy applied to the heater material is reduced, and an appropriate applied voltage of 1.2 Vth cannot be obtained. That is, as the heater resistance increases, the heater energy decreases, so the amount of ejected ink gradually decreases.
When it reaches%, it becomes impossible to discharge. Actual N ₂ partial pressure ratio 30
%, X-ray diffraction pattern (III) recording head is ΔR1
At 0%, a change in image quality from the initial quality was recognized.

Next, the tantalum nitride film having an N ₂ partial pressure ratio of 20% and an X-ray diffraction pattern (I) has a resistance change rate of −5.0.
It is a negative percentage. On the positive side of the resistance change rate, the energy given to the heater is relatively reduced, which is advantageous for the life, but on the negative side, the energy is increased, which is disadvantageous for the life.
Particularly in printing by a printer, positive resistance is a problem of quality, but disconnection at the time of minus is a serious problem in terms of image quality because a specific nozzle does not discharge and characters cannot be judged.

In practice, the tantalum nitride film having a N ₂ partial pressure ratio of 20% is broken in about 400 prints and practically difficult to use. By the way, the rank of image quality in Table 3 is
The image quality after recording 1000 sheets was able to maintain a good condition that was almost equal to or better than the initial one, and ○ was less than the initial, but was at a level where there was no problem in practical use. It was evaluated based on the criterion that what was seen was x.

According to the evaluation as the ink jet film described in Table 3 above, the tantalum nitride film formed by the reactive sputtering method using the mixed gas of Ar and N ₂ is N
_The partial pressure ratio is 22 to 26%, the composition ratio is Ta in a molar weight ratio based on N of 1.4 or more and 1.9 or less, and the film crystallinity by X-ray diffraction measurement is as shown in FIG. 8 (101). Hexagonal Ta ₂ N in orientation and hexagonal T in (110) orientation
It has been found that a mixed film of aN has high performance as a heating resistor for inkjet. Even if parameters such as N ₂ partial pressure ratio, Ar + N ₂ mixed gas pressure, DC power, and substrate temperature, which are film forming conditions for reactive sputtering, were changed, a tantalum nitride film showing the above composition ratio and crystallinity was formed. It was also found that the film can be evaluated as an equivalent inkjet heating resistor.

(Embodiment 2) FIG. 1 shown in the above embodiment.
Using the same recording head substrate as above, a tantalum nitride film, which is the heating resistor 103, was formed by a sputtering target sputtering method. This sintering target is produced by the hot pressing method and has an impurity concentration of several ppm or less. Table 2 shows the composition of the tantalum nitride film formed by using the sintering targets having various compositions; the resistivity and the result of the X-ray diffraction measurement.

Before sputtering, first, R
The base film and the contact portion of the heating resistor were etched by tens of liters by f sputtering to obtain a clean surface.

After that, the pressure of the Ar gas atmosphere is adjusted to 5 to 10
After setting the substrate temperature in mTr to 200 to 300 ° C.,
DC power of 1.0 to 3.0 kw is applied.

These series of film forming processes were carried out in a high vacuum without exposing to the atmosphere, as in the above-mentioned embodiment.

As shown in Table 2, as the composition ratio of air in the sintered body increases, the proportion of N in the film also increases, and the resistivity ρ also increases accordingly. The reason why the specific resistance corresponding to the composition ratio in Table 1 shown in the above-mentioned examples is slightly higher is considered to be due to impurities contained in the hot pressing. Table 2 shows the main diffraction peak patterns of the tantalum nitride film measured by X-ray diffraction. The film composition ratio is Ta in a molar weight ratio of 1.8 to 2.
The film in the range of 0 exhibits orientation in the hexagonal Ta ₂ N (002) and hexagonal Ta ₂ N (101) orientations, and Ta is 1.4
Films in the range of ˜1.9 exhibit hexagonal Ta ₂ N (101) and hexagonal TaN (110) orientation. Also, Ta
The film with a ratio of 1.0 to 1.3 has hexagonal TaN (11
0) and hexagonal TaN (101) orientation.
The above three types of characteristic tantalum nitride film orientations are classified into patterns (IV), (V), and (VI) in order, and the measurement results are shown in FIGS. 10, 11, and 12.

Table 4 shows the results of a study on film quality evaluation as an ink jet head manufactured using tantalum nitride heat generating resistors formed by sintering targets in various composition ratios. The examination method is the same as the method described in Example 1. From Table 4, the film composition TaxN; 1.4 ≦
x ≦ 1.7, the tantalum nitride film of the X-ray diffraction pattern (V) exhibits a high Kb value of 1.7 to 1.8, and the film composition ratio of 1.8 ≦
x ≦ 2.0, X-ray diffraction pattern (IV) and 1.0 ≦ x
The film having an X-ray diffraction pattern (VI) of ≦ 1.3 showed a lower value than the tantalum nitride film having the above composition ratio.

Further, similarly to the breaking voltage Kb, in Table 4, the tantalum nitride film having the above composition ratio having a high Kb value shows a small resistance change rate value, and at the time of 1000 sheets, −2.0 to +2.
It was found to be 5, which is a level with no practical problems. or,
Film composition TaxN; 1.8 ≦ x ≦ 2.0, film having X-ray diffraction pattern (IV), resistance change rate reaches a value of approximately + 10%, and discharge occurs as the heater energy decreases. There was a change in quality. Film composition 1.0 ≦ x ≦
1.3, the film of X-ray diffraction pattern (VI) showed a resistance change rate of around -5%, and a breakage occurred due to an increase in heater energy before and after printing 400 sheets.

According to the evaluation as the ink jet film described in Table 4 above, the tantalum nitride film which is the heating resistor 103 formed by the sputtering method using the tantalum nitride sintered target has a film composition ratio of N. Ta is 1.4 or more and 1.9 or less in terms of molar weight ratio based on
The film crystallinity by X-ray diffraction is hexagonal T as shown in FIG.
It has been found that a mixed film having an a ₂ N (101) orientation and a hexagonal TaN (110) orientation has high performance as a heating resistor for inkjet.

[0069]

[Table 1]

[0070]

[Table 2]

[0071]

[Table 3]

[0072]

[Table 4]

(Comparative Example 1) The heat generating resistance layer 103 of the substrate of the liquid jet recording head in the example was replaced with R instead of TaN.
HfB ₂ was deposited to a thickness of 0.1 μm by the F sputtering method, and an ink jet head was manufactured in the same manner as in the above example.

In FIG. 13, a rectangular voltage of 7 μs was applied to the electrothermal converter at about 10 ⁵ pulses at 2 KHz, and every 10 0.02 Vth, in the same manner as in the case of measuring the breaking voltage described above using this ink jet head. When increasing the applied voltage, the resistance value was measured each time, and the change in resistance value until the electrothermal converter was broken was shown.

The change in resistance in the figure shows the change between the heating resistor made of HfB _{2 of} Comparative Example 1 and the heating resistor made of TaN of Example 1 above.

[0076] those commonly a HfB ₂ was heating resistor, exhibit excellent properties of a heat resisting HfB _2. However, the electrothermal converter using TaN according to the present invention could have a breakdown voltage ratio of about 1.8, which is higher than HfB ₂ of 1.6.

As described above, HfB excellent as a normal resistor is obtained.
_The fact that the tantalum nitride films of both Examples 1 and 2 exceeded 2 was that the crystal structure of the tantalum nitride film was excellent in terms of heat and mechanical properties, as shown in Examples 1 and 2, and nitrogen and tantalum This is because the composition ratio of is located in an energy stable region. Since these characteristics are common to the above-mentioned embodiment, even if the manufacturing method of the above tantalum nitride film which is a stable heating resistor is different, the formed tantalum nitride film is described in the above-mentioned embodiment. X-ray diffraction pattern (I
If the composition ratios of I) and (IV) are shown, it suggests that the inkjet heating resistor has high performance.

[0078]

As described above, according to the present invention, the composition and crystal of the tantalum nitride film, which has been conventionally insufficient in durability against the use of a short pulse, for the heating resistor used in the ink jet head. It is possible to obtain excellent characteristics by setting the characteristics in a certain area. Further, in the above effects of the present invention, the production method is a reactive sputtering method,
Sputtering method using sintered target or C
It has been found that the formed tantalum nitride film maintains the above-mentioned film quality even if the VD method and the like are different, and that the tantalum nitride film always exhibits the same characteristics if it is contained in a region having a composition and crystallinity.

Therefore, according to the use or cost,
It has become possible to stably manufacture a heating resistor, an inkjet head substrate, and an inkjet head, which have high reliability, high uniformity, high-definition recording, and high-speed recording.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view showing a recording head substrate manufactured according to the present invention.

FIG. 2 is a schematic cross-sectional view of electrodes of a recording head substrate.

FIG. 3 is a schematic plan view of electrodes of a recording head substrate.

FIG. 4 is a schematic cross-sectional view of an electrothermal conversion element portion of a recording head substrate.

FIG. 5 is a schematic plan view of an electrothermal conversion element portion of a recording head substrate.

FIG. 6 is a diagram for explaining the specific resistance and composition ratio of the heating resistor according to the present invention.

FIG. 7 is a diagram illustrating an X-ray diffraction pattern of a heating resistor.

FIG. 8 is a diagram illustrating an X-ray diffraction pattern of a heating resistor.

FIG. 9 is a diagram illustrating an X-ray diffraction pattern of a heating resistor.

FIG. 10 is a diagram illustrating an X-ray diffraction pattern of a heating resistor.

FIG. 11 is a diagram illustrating an X-ray diffraction pattern of a heating resistor.

FIG. 12 is a diagram illustrating an X-ray diffraction pattern of a heating resistor.

FIG. 13 is a diagram for explaining the effect of the present invention.

FIG. 14 is a schematic assembly diagram of a conventional inkjet head.

15 is a schematic cross-sectional view of the inkjet head of FIG.

[Description of Reference Signs] 1 P-type silicon substrate 2 N-type collector buried region 3 P-type isolation buried region 4 N-type epitaxial region 5 P-type base region 6 P-type isolation region 7 N-type collector region 8 High concentration P Type base region 9 High concentration P type isolation region 10 High concentration N type emitter region 11 High concentration N type collector region 12 Collector / base common electrode 13 Emitter electrode 14 Isolation electrode 101 Thermal storage layer 102 Interlayer film 103 Heating resistance layer 104 Wiring Electrode 105 First protective film 106 Second protective film 110 Heat generating part

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Claims (30)

[Claims] 1. A heating resistor having tantalum nitride, wherein the tantalum nitride has a plane orientation of (10) by X-ray diffraction.
1) Ta ₂ N showing a peak of orientation and a plane orientation of (110)
A heating resistor having TaN showing a peak of orientation. 2. The heating resistor according to claim 1, wherein the crystal of tantalum nitride is a hexagonal crystal. 3. The heating resistor according to claim 1, wherein the tantalum nitride has a molar weight ratio based on nitrogen of 1.4 or more and 1.9 or less. 4. An electric / thermal conversion comprising a substrate, a layer of a heating resistor formed on the substrate, and a pair of electrodes electrically connected to the layer of the heating resistor with a gap therebetween. An inkjet head substrate having at least an element, comprising:
The layer of the heating resistor has a plane orientation of (10
1) A substrate for an inkjet head, which is formed of tantalum nitride having Ta ₂ N showing a peak of orientation and TaN showing a peak of (110) orientation. 5. The inkjet head substrate according to claim 4, wherein the crystal of tantalum nitride is a hexagonal crystal. 6. The inkjet head substrate according to claim 4, wherein the tantalum nitride has a molar weight ratio based on nitrogen of 1.4 or more and 1.9 or less. 7. The inkjet head substrate according to claim 4, wherein the substrate is a semiconductor substrate. 8. The inkjet head substrate according to claim 7, wherein the semiconductor substrate has a driving element for driving the electrothermal conversion element. 9. The inkjet head substrate according to claim 8, wherein the driving element has a transistor. 10. The inkjet head substrate according to claim 4, wherein a plurality of the electric / heat conversion elements are provided and arranged in an array. 11. An electrothermal conversion comprising a substrate, a heating resistor layer formed on the substrate, and a pair of electrodes electrically connected to the heating resistor layer with a gap therebetween. In an inkjet head having an element, a liquid path provided corresponding to the gap, and an opening provided at least a part of the liquid path corresponding to the gap, the layer of the heating resistor is The plane orientation by X-ray diffraction is Ta ₂ N showing a peak of (101) orientation and Ta showing a peak of (110) orientation.
An ink jet head formed of tantalum nitride containing N. 12. The ink jet head according to claim 11, wherein the crystal of tantalum nitride is a hexagonal crystal. 13. The ink jet head according to claim 11, wherein the tantalum nitride has a molar weight ratio based on nitrogen of 1.4 or more and 1.9 or less. 14. The substrate is a semiconductor substrate.
1. The inkjet head according to 1. 15. The ink jet head according to claim 14, wherein the semiconductor substrate has a driving element for driving the electrothermal conversion element. 16. The ink jet head according to claim 15, wherein the driving element has a transistor. 17. The inkjet head substrate according to claim 11, wherein a plurality of the electric / heat conversion elements are provided and arranged in an array. 18. The ink jet head according to claim 11, wherein the electrothermal converter has a protective layer on the liquid path side. 19. The ink jet head according to claim 11, further comprising a plurality of the liquid passages, and a common liquid chamber to which the plurality of liquid passages are commonly connected. 20. A method of manufacturing a heating resistor having tantalum nitride, wherein the tantalum nitride has Ta ₂ N and (11) which have a peak of (101) orientation in a plane orientation by X-ray diffraction.
0) A method for manufacturing a heating resistor, which has TaN exhibiting a peak of orientation, and the tantalum nitride is formed by a reactive sputtering method or a sputtering method. 21. The method for producing a heating resistor according to claim 20, wherein the reactive sputtering method is performed in an atmosphere containing a tantalum target and an argon gas and a nitrogen gas. 22. The partial pressure ratio of the nitrogen gas is 20 to 30%
22. The method for manufacturing a heating resistor according to claim 21, wherein 23. The method of manufacturing a heating resistor according to claim 21, wherein the temperature of the substrate on which the heating resistor is formed is in the range of 200 ° C. to 300 ° C. 24. The method of manufacturing a heating resistor according to claim 21, wherein the pressure of the atmosphere is 5 to 10 mTr. 25. The method of manufacturing a heating resistor according to claim 20, wherein the sputtering is performed in an atmosphere containing argon gas using a target containing tantalum and nitrogen. 26. The method for manufacturing a heating resistor according to claim 25, wherein the temperature of the substrate on which the heating resistor is formed is in the range of 200 ° C. to 300 ° C. 27. The pressure of the argon gas atmosphere is 5
27. The method for manufacturing a heating resistor according to claim 25 or 26, wherein the heating resistor is 10 mTr. 28. The surface of a substrate on which the heating resistor is formed is etched before the heating resistor is formed.
28. A method of manufacturing a heating resistor according to any one of items 27 to 27. 29. The method of manufacturing a heating resistor according to claim 28, wherein the etching is performed by an Rf sputtering method. 30. The method of manufacturing a heating resistor according to claim 20, wherein the heating resistor is manufactured under an ultrahigh vacuum.