JPH0572474B2 - - Google Patents
Info
- Publication number
- JPH0572474B2 JPH0572474B2 JP15081286A JP15081286A JPH0572474B2 JP H0572474 B2 JPH0572474 B2 JP H0572474B2 JP 15081286 A JP15081286 A JP 15081286A JP 15081286 A JP15081286 A JP 15081286A JP H0572474 B2 JPH0572474 B2 JP H0572474B2
- Authority
- JP
- Japan
- Prior art keywords
- substrate
- deposited
- molecules
- ultra
- electron beam
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000758 substrate Substances 0.000 claims description 36
- 239000000463 material Substances 0.000 claims description 31
- 238000010894 electron beam technology Methods 0.000 claims description 16
- 239000010409 thin film Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- 238000001179 sorption measurement Methods 0.000 claims description 7
- 239000000470 constituent Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 description 20
- 239000010408 film Substances 0.000 description 10
- 238000010586 diagram Methods 0.000 description 6
- 230000001678 irradiating effect Effects 0.000 description 6
- 238000003860 storage Methods 0.000 description 5
- 239000011651 chromium Substances 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910003902 SiCl 4 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- -1 tungsten (W) Chemical class 0.000 description 1
- NXHILIPIEUBEPD-UHFFFAOYSA-H tungsten hexafluoride Chemical compound F[W](F)(F)(F)(F)F NXHILIPIEUBEPD-UHFFFAOYSA-H 0.000 description 1
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- Chemical Vapour Deposition (AREA)
- Electrodes Of Semiconductors (AREA)
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、電子ビーム照射による超薄膜形成方
法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method of forming an ultra-thin film by electron beam irradiation.
［従来の技術］
従来、基板上に吸着層分の極薄膜を形成させる
方法としては、第３図ａ，ｂに示す工程によつて
行われている。すなわち、まず第３図ａに示すよ
うに、超高真空内に基板３２を置き、基板３２表
面を清浄化した後、堆積させるべき材料中の少な
くとも一部の元素を構成元素として含む１種また
は２種以上のガスを被堆積基板上に流し、前記ガ
ス分子を被堆積基板上に吸着させて吸着分子３１
とする。[Prior Art] Conventionally, a method of forming an extremely thin film for an adsorption layer on a substrate has been carried out by the steps shown in FIGS. 3a and 3b. That is, as shown in FIG. 3a, first, the substrate 32 is placed in an ultra-high vacuum, the surface of the substrate 32 is cleaned, and then one or more of the constituent elements containing at least some of the elements in the material to be deposited are deposited. Two or more gases are flowed onto the substrate to be deposited, and the gas molecules are adsorbed onto the substrate to form adsorbed molecules 31.
shall be.
次に、第３図ｂに示すように、吸着分子３１を
解離させる光エネルギーを有する光を基板に照射
することにより、雰囲気ガス吸着分子３１はその
中に含まれる堆積材料３３と揮発性材料分子３４
とに分解し、堆積材料３３は基板表面に析出す
る。一方、揮発性材料分子３４は真空排出され
る。以上の様な原理により基板３２表面上に光照
射により吸着層分の超薄膜が形成される。 Next, as shown in FIG. 3b, by irradiating the substrate with light having optical energy that dissociates the adsorbed molecules 31, the atmospheric gas adsorbed molecules 31 are separated from the deposited material 33 and volatile material molecules contained therein. 34
The deposited material 33 is deposited on the substrate surface. Meanwhile, the volatile material molecules 34 are evacuated. According to the principle described above, an ultra-thin film equivalent to an adsorption layer is formed on the surface of the substrate 32 by light irradiation.
［発明が解決しようとする問題点］
ところが、上記のような従来の方法によるとき
には、吸着分子３１を解離するのに要する光の適
切な波長（エネルギー）があり、任意の材料を堆
積させることは困難であり、また光としてレーザ
を用いても、その分解能は波長により制限され線
幅1μｍ以下のパターンを堆積させることは困難
であるなどの問題があつた。[Problems to be Solved by the Invention] However, when using the conventional method as described above, there is an appropriate wavelength (energy) of light required to dissociate the adsorbed molecules 31, and it is difficult to deposit any material. Furthermore, even if a laser is used as the light, its resolution is limited by the wavelength, making it difficult to deposit a pattern with a line width of 1 μm or less.
本発明の目的は、任意の材料を基板上に堆積さ
せることができ、しかも高精度かつ高分解能の吸
着層分の超薄膜パターンを作製することも可能な
超薄膜形成方法を提供することにある。 An object of the present invention is to provide an ultra-thin film forming method that allows any material to be deposited on a substrate and also allows for the creation of an ultra-thin film pattern for an adsorption layer with high precision and high resolution. .
［問題点を解決するための手段］
本発明は、堆積させるべき材料中に含まれる少
なくとも一部の元素を構成元素として含む１種ま
たは２種以上のガス状分子を被堆積基板上に流
し、このガス状分子を被堆積基板上に吸着させた
のち真空排気し、次いで基板の所望の部分に電子
ビームを照射して前記材料を基板上に吸着層分だ
け堆積させることを特徴とする超薄膜形成方法で
ある。[Means for Solving the Problems] The present invention provides a method of flowing one or more gaseous molecules containing as constituent elements at least some of the elements contained in the material to be deposited onto a substrate to be deposited; This ultra-thin film is characterized by adsorbing the gaseous molecules onto the substrate to be deposited, evacuation, and then irradiating a desired portion of the substrate with an electron beam to deposit the material on the substrate in an amount equivalent to the adsorbed layer. This is the formation method.
本発明において堆積させるべき材料としてはタ
ングステン（Ｗ）、モリブデン（Mo）、アルミニ
ウム（Al）、クロム（Cr）、タンタル（Ta）、チ
タン（Ti）、ジルコニウム（Zr）等の金属やケイ
素（Si）のような各種元素のほか酸化ケイ素
（SiO2）、窒化チタン（TiN）、酸化タンタル
（Ta2O5）のような分子があげられる。 Materials to be deposited in the present invention include metals such as tungsten (W), molybdenum (Mo), aluminum (Al), chromium (Cr), tantalum (Ta), titanium (Ti), and zirconium (Zr), and silicon (Si). ), as well as molecules such as silicon oxide (SiO 2 ), titanium nitride (TiN), and tantalum oxide (Ta 2 O 5 ).
これらの材料を堆積させるための雰囲気ガス
は、前記材料中に含まれる少なくとも一部の元素
を構成元素として含む１種又は２種以上のガス状
分子であり、堆積材料がＷの場合にはWF6、
WCl6、WCl5、WBr5等、Moの場合にはMo
（C6H6）2、MoCl5、MoBr5等、Alの場合にはAl
（CH3）3等、Crの場合にはCr（C6H6）2等、Taの場
合にはTaCl5、TaBr5等、Tiの場合にはTiI4等、
Zrの場合にはZrI4等が挙げられる。 The atmospheric gas for depositing these materials is one or more gaseous molecules containing at least some of the elements contained in the materials as constituent elements, and when the deposition material is W, WF 6 ,
WCl 6 , WCl 5 , WBr 5 etc., Mo in case of Mo
(C 6 H 6 ) 2 , MoCl 5 , MoBr 5 etc., in the case of Al, Al
(CH 3 ) 3 , etc., for Cr, Cr(C 6 H 6 ) 2 , etc., for Ta, TaCl 5 , TaBr 5 , etc., for Ti, TiI 4 , etc.
In the case of Zr, examples include ZrI 4 and the like.
また雰囲気ガスとしてSiH4、SiH2Cl2、SiCl4
等を用いればSi膜を堆積できる。又、SiH4と
NH3との混合ガスを用いれば、Si3N4膜を、又
SiH4とO2との混合ガスを用いれば、SiO2膜を形
成することができる。又、TiCl4とN2との混合ガ
スを用いるとTiN膜を形成することができる。 In addition, SiH 4 , SiH 2 Cl 2 , and SiCl 4 are used as atmospheric gases.
A Si film can be deposited using, for example, Also, SiH 4 and
If a mixed gas with NH 3 is used, Si 3 N 4 film or
A SiO 2 film can be formed using a mixed gas of SiH 4 and O 2 . Furthermore, a TiN film can be formed using a mixed gas of TiCl 4 and N 2 .
又、Si（OC2H5）4を用いればSiO2、Ta
（OC2H5）5を用いれば、Ta2O5が形成できる。 Also, if Si(OC 2 H 5 ) 4 is used, SiO 2 , Ta
If (OC 2 H 5 ) 5 is used, Ta 2 O 5 can be formed.
本発明の方法によつて得られる超薄膜は、通常
単分子膜あるいは２〜３分子層の膜であり、従つ
てその膜厚は通常５〜15Åである。また収束され
た電子ビームを照射することによつてナノメータ
レベルの極細線幅のパターン形成が可能である。 The ultra-thin film obtained by the method of the present invention is usually a monomolecular film or a film of 2 to 3 molecular layers, and therefore the film thickness is usually 5 to 15 Å. Furthermore, by irradiating with a focused electron beam, it is possible to form a pattern with an extremely fine line width on the nanometer level.
［作用］
次に、本発明の作用について、第１図を用いて
説明する。すなわち、第１図ａでは、超高真空内
に基板１２を置き、基板１２表面を洗浄化した
後、堆積させるべき材料中に含まれる少なくとも
一部の元素を構成元素として含んだ１種または２
種以上のガスを被堆積基板上に流し、前記ガス分
子を被堆積基板１２上に吸着させて吸着分子１１
とする。次に、第１図ｂに示す様に、収束した電
子ビームを基板に照射することにより、照射され
た吸着分子１１はその中に含まれる堆積材料１３
と揮発性材料分子１４とに分解し、堆積材料１３
は、基板１２表面に析出する。一方、揮発性材料
分子１４は排出される。以上のような原理によ
り、基板１２表面上に、電子ビーム照射により、
吸着層分の超薄膜パターンが形成される。[Function] Next, the function of the present invention will be explained using FIG. 1. That is, in FIG. 1a, the substrate 12 is placed in an ultra-high vacuum, and after cleaning the surface of the substrate 12, one or two of the constituent elements containing at least some of the elements contained in the material to be deposited are deposited.
More than one species of gas is caused to flow onto the substrate to be deposited, and the gas molecules are adsorbed onto the substrate to be deposited 12 to form adsorbed molecules 11.
shall be. Next, as shown in FIG. 1b, by irradiating the substrate with a focused electron beam, the irradiated adsorbed molecules 11 are absorbed into the deposited material 13 contained therein.
and volatile material molecules 14, depositing material 13
is deposited on the surface of the substrate 12. On the other hand, volatile material molecules 14 are discharged. According to the above principle, the surface of the substrate 12 is irradiated with an electron beam,
An ultra-thin film pattern corresponding to the adsorption layer is formed.
［実施例］
以下に本発明の実施例について、図面を参照し
て説明する。第２図は本発明の一実施例で用いる
装置の構成を示す概略図である。本装置は電子ビ
ーム照射系２０７〜２０９、試料室２０６、及び
雰囲気ガス材料収納室２０１とから構成されてい
る。本実施例においては、タングステン（Ｗ）を
構成元素として含む六フツ化タングステン
（WF6）を雰囲気ガスとして用い、収束された電
子ビーム照射によりケイ素（Si）基板上にＷを堆
積させた。[Examples] Examples of the present invention will be described below with reference to the drawings. FIG. 2 is a schematic diagram showing the configuration of an apparatus used in an embodiment of the present invention. This apparatus is composed of electron beam irradiation systems 207 to 209, a sample chamber 206, and an atmospheric gas material storage chamber 201. In this example, tungsten hexafluoride (WF 6 ) containing tungsten (W) as a constituent element was used as an atmospheric gas, and W was deposited on a silicon (Si) substrate by focused electron beam irradiation.
WF6２０２を雰囲気ガス材料収納室２０１に
入れ、Ｗを堆積させるSi基板２０５を試料台２０
４にセツトする。電子ビーム照射系２０７〜２０
９と試料室２０６を10-10Torr以下の超高真空に
排気すると共に、試料室２０６を800℃以上に加
熱することにより基板表面を清浄化する。試料室
２０６と雰囲気ガス材料収納室２０１とは配管２
０３によつて接続されており、試料室２０６を真
空排気することにより、雰囲気ガス材料収納室２
０１内部が真空排気される。雰囲気ガス材料であ
るWF6は大気中では液体であるが真空にひくこ
とにより、容易に昇華し、配管２０３を通り、マ
スフローメータ２１１を通して試料室２０６内部
へ供給される。ガス流量は、マスフローメータ２
１１により制御される。このようにして、Si基板
２０５上にWF6分子が吸着する。その後、マス
フローメータを閉じ、試料室２０６内へのWF6
ガスの供給を止めた後、試料室２０６を超高真空
まで排気する。次に、電子ビームをSi基板２０５
の所望の部分に照射することにより、Si基板２０
５表面上に吸着されたWF6分子を分解する。そ
の分解の結果、WF6分子はＷとフツ素（F2）に
分かれる。不揮発性物質であるＷはSi基板２０５
上に析出する。一方F2は揮発性ガスであるので
真空排気される。このようにして、吸着層分のＷ
がSi基板２０５表面の所望の部分に堆積する。 WF 6 202 is placed in the atmosphere gas material storage chamber 201, and the Si substrate 205 on which W is to be deposited is placed on the sample stage 20.
Set to 4. Electron beam irradiation system 207-20
9 and the sample chamber 206 are evacuated to an ultra-high vacuum of 10 −10 Torr or less, and the sample chamber 206 is heated to 800° C. or higher to clean the substrate surface. The sample chamber 206 and the atmospheric gas material storage chamber 201 are connected to the piping 2.
03, and by evacuating the sample chamber 206, the atmospheric gas material storage chamber 2
The inside of 01 is evacuated. Although the atmospheric gas material WF 6 is a liquid in the atmosphere, it is easily sublimed in a vacuum, and is supplied to the inside of the sample chamber 206 through the pipe 203 and the mass flow meter 211 . Gas flow rate is measured using mass flow meter 2.
11. In this way, WF 6 molecules are adsorbed onto the Si substrate 205. After that, the mass flow meter is closed, and the WF 6 flows into the sample chamber 206.
After stopping the gas supply, the sample chamber 206 is evacuated to ultra-high vacuum. Next, the electron beam is applied to the Si substrate 205.
By irradiating a desired portion of the Si substrate 20
5 decomposes the WF 6 molecules adsorbed on the surface. As a result of its decomposition, the WF 6 molecule separates into W and fluorine (F 2 ). W, which is a non-volatile substance, is on the Si substrate 205
It precipitates on top. On the other hand, since F2 is a volatile gas, it is evacuated. In this way, W for the adsorption layer is
is deposited on a desired portion of the surface of the Si substrate 205.
このようにして電子ビーム露光と同様のビーム
制御技術を用い、ナノメータレベル極細線幅を十
分制御して、吸着層分の膜厚をもつた超薄膜パタ
ーンを形成することができる。 In this way, using a beam control technique similar to electron beam exposure, it is possible to sufficiently control the nanometer-level ultrafine line width and form an ultrathin film pattern with a film thickness equal to that of the adsorption layer.
なお、この実施例では収束された電子ビームを
用いたが、収束されていない電子ビームを用いて
も良い。この場合には広い面積に超薄膜が形成さ
れる。 Note that although a focused electron beam is used in this embodiment, a non-focused electron beam may also be used. In this case, an ultra-thin film is formed over a wide area.
［発明の効果］
以上説明したように、本発明によれば、堆積材
料を含む分子を吸着させた基板表面に電子ビーム
を照射することにより任意の材料について吸着層
分の厚みを有した超薄膜を形成させることができ
る。[Effects of the Invention] As explained above, according to the present invention, by irradiating an electron beam onto the surface of a substrate on which molecules containing a deposited material are adsorbed, an ultra-thin film having the thickness of an adsorbed layer of any material can be formed. can be formed.
第１図は本発明の方法による超薄膜形成を膜式
的に示した図で第１図ａは基板上に吸着分子が吸
着された状態を示す図、第１図ｂはこの基板に電
子ビームを照射した時の状態を示す図であり、第
２図は本発明の方法を実施するための装置の一例
を示す概略図、第３図は従来の超薄膜形成方法を
模式的に示した図で、第３図ａは基板に吸着分子
が吸着された状態を示す図、第３図ｂはこの基板
に光を照射した時の状態を示す図である。
１１，３１……吸着分子、１２，３２，２０５
……基板、１３，３３……堆積材料、１４，３４
……揮発性材料分子、２０１……雰囲気ガス材料
収納室、２０２……WF6、２０３……配管、２
０４……試料台、２０６……試料室、２０７，２
０８，２０９……電子ビーム照射系、２１０……
電子ビーム、２１１……マスフローメータ。
Figure 1 is a diagram showing the formation of an ultra-thin film by the method of the present invention in film form. FIG. 2 is a schematic diagram showing an example of an apparatus for carrying out the method of the present invention, and FIG. 3 is a diagram schematically showing a conventional ultra-thin film forming method. FIG. 3a is a diagram showing a state in which adsorbed molecules are adsorbed on a substrate, and FIG. 3b is a diagram showing a state in which this substrate is irradiated with light. 11,31... adsorbed molecule, 12,32,205
...Substrate, 13,33...Deposited material, 14,34
... Volatile material molecules, 201 ... Atmospheric gas material storage chamber, 202 ... WF 6 , 203 ... Piping, 2
04... Sample stand, 206... Sample chamber, 207,2
08,209...Electron beam irradiation system, 210...
Electron beam, 211...Mass flow meter.
Claims (1)
一部の元素を構成元素として含む１種または２種
以上のガス状分子を被堆積基板上に流し、このガ
ス状分子を被堆積基板上に吸着させたのち真空排
気し、次いで基板の所望の部分に電子ビームを照
射して前記材料を基板上に吸着層分だけ堆積させ
ることを特徴とする超薄膜形成方法。1. One or more gaseous molecules containing as constituent elements at least some of the elements contained in the material to be deposited are flowed onto the substrate to be deposited, and these gaseous molecules are adsorbed onto the substrate to be deposited. A method for forming an ultra-thin film, characterized in that the material is then evacuated, and then a desired portion of the substrate is irradiated with an electron beam to deposit the material on the substrate in an amount corresponding to the adsorption layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15081286A JPS637372A (en) | 1986-06-26 | 1986-06-26 | Formation of extra-thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15081286A JPS637372A (en) | 1986-06-26 | 1986-06-26 | Formation of extra-thin film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS637372A JPS637372A (en) | 1988-01-13 |
| JPH0572474B2 true JPH0572474B2 (en) | 1993-10-12 |
Family
ID=15504956
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15081286A Granted JPS637372A (en) | 1986-06-26 | 1986-06-26 | Formation of extra-thin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS637372A (en) |
-
1986
- 1986-06-26 JP JP15081286A patent/JPS637372A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS637372A (en) | 1988-01-13 |
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