JPS63145779A - Method for controlling stress of hexagonal boron nitride film - Google Patents
Method for controlling stress of hexagonal boron nitride filmInfo
- Publication number
- JPS63145779A JPS63145779A JP61292060A JP29206086A JPS63145779A JP S63145779 A JPS63145779 A JP S63145779A JP 61292060 A JP61292060 A JP 61292060A JP 29206086 A JP29206086 A JP 29206086A JP S63145779 A JPS63145779 A JP S63145779A
- Authority
- JP
- Japan
- Prior art keywords
- boron nitride
- substrate
- nitride film
- hexagonal boron
- thermal expansion
- 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.)
- Pending
Links
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 229910052582 BN Inorganic materials 0.000 title claims abstract description 112
- 238000000034 method Methods 0.000 title claims description 39
- 239000000758 substrate Substances 0.000 claims abstract description 91
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000000151 deposition Methods 0.000 claims abstract description 16
- 150000001639 boron compounds Chemical class 0.000 claims description 12
- 229910017464 nitrogen compound Inorganic materials 0.000 claims description 10
- 150000002830 nitrogen compounds Chemical class 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 9
- 230000002040 relaxant effect Effects 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 15
- 238000001015 X-ray lithography Methods 0.000 abstract description 13
- 229910052796 boron Inorganic materials 0.000 abstract description 13
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 239000012159 carrier gas Substances 0.000 abstract description 3
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical compound [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 abstract 1
- 239000010408 film Substances 0.000 description 72
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 24
- 230000008021 deposition Effects 0.000 description 12
- 229910021529 ammonia Inorganic materials 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000010586 diagram Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- BGECDVWSWDRFSP-UHFFFAOYSA-N borazine Chemical group B1NBNBN1 BGECDVWSWDRFSP-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- -1 boron halides Chemical class 0.000 description 2
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910052594 sapphire Inorganic materials 0.000 description 2
- 239000010980 sapphire Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- YPSXFMHXRZAGTG-UHFFFAOYSA-N 4-methoxy-2-[2-(5-methoxy-2-nitrosophenyl)ethyl]-1-nitrosobenzene Chemical compound COC1=CC=C(N=O)C(CCC=2C(=CC=C(OC)C=2)N=O)=C1 YPSXFMHXRZAGTG-UHFFFAOYSA-N 0.000 description 1
- 102100021569 Apoptosis regulator Bcl-2 Human genes 0.000 description 1
- 229910052580 B4C Inorganic materials 0.000 description 1
- 229910015845 BBr3 Inorganic materials 0.000 description 1
- 101000971171 Homo sapiens Apoptosis regulator Bcl-2 Proteins 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000000427 thin-film deposition Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000000411 transmission spectrum Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/22—Masks or mask blanks for imaging by radiation of 100nm or shorter wavelength, e.g. X-ray masks, extreme ultraviolet [EUV] masks; Preparation thereof
Abstract
Description
【発明の詳細な説明】
「産業上の利用分野」
この発明は、Ｘ線リソグラフィにおけるマスク基板等に
使用される六方晶窒化硼素膜の応力制御方法に関する。DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention relates to a method for controlling stress in a hexagonal boron nitride film used as a mask substrate in X-ray lithography.
「従来の技術」
近年、半導体製造技術の微細化の傾向の一つとして、い
わゆるサブミクロン領域での＠細加工技術が脚光を浴び
ている。この微細加工技術は、大別して電子線によるし
の、イオンビームによるもの、また、Ｘ線によるものが
挙げられるが、とりわけｘｉによる微細加工技術（以下
、Ｘ線リソグラフィと称する）は、照射するＸ線の波長
が短い（敗入〜数十人程度）ため、０．１μ麓程度まで
の微細なパターンを基板上に形成することが可能である
という利点を有し、注目を集めている。"Conventional Technology" In recent years, as one of the trends toward miniaturization of semiconductor manufacturing technology, @fine processing technology in the so-called submicron region has been in the spotlight. This microfabrication technology can be roughly divided into those using electron beams, those using ion beams, and those using X-rays. In particular, microfabrication technology using xi (hereinafter referred to as X-ray lithography) is Since the wavelength of the line is short (about a few dozen lines), it has the advantage of being able to form fine patterns down to about 0.1 μm on a substrate, and is attracting attention.
前記Ｘ線リソグラフ、ｆに使用され、その表面に転写用
原パターンが形成されるマスク基板は、前記Ｘ線が十分
に透過される必要があるため、その材料となる物質は軽
元素に限定される。また、Ｘ線マスク基板に要求される
他の条件としては、以下に示すようなものが挙げられろ
。The mask substrate used in the X-ray lithography, on which the original pattern for transfer is formed, needs to be sufficiently penetrated by the X-rays, so its material is limited to light elements. Ru. Further, other conditions required for the X-ray mask substrate include the following.
（１） レジストの最高感度の領域でＸ線源に対して透
明であること。(1) Be transparent to the X-ray source in the most sensitive area of the resist.
（２）取り扱いの点でも、パターンを形成するためにも
適当な強度を有すること。(2) It must have appropriate strength both in terms of handling and in forming patterns.
（３）基板上にパターン等を作製する工程を考え、熱的
にも化学的にも安定であること。(3) Considering the process of creating patterns etc. on the substrate, it must be thermally and chemically stable.
（４） Ｘｉの照射に対して安定であること。(4) It must be stable against Xi irradiation.
（５）可視光の範囲でマスクの重ね合わせを可能にする
ため光学的に透明であること。(5) be optically transparent to allow mask overlay in the visible light range;
（６）マスクパターンを形成するために許容できる範囲
内で表面が平坦であること。(6) The surface is flat within an allowable range for forming a mask pattern.
以上の要求を満足する物質として、従来半導体製造に使
用されているシリコン（’Ｓｉ ）基板の他に、窒化
硼素（ＢＮ）、炭化硼素（Ｂ、Ｃ）、珪化硼素（Ｂ４Ｓ
ｌ）等の硼化物によるＸ線リソグラフィ用のマスク基板
が近年提案されている（例えば特公昭５６−３７６９２
号明細書）。In addition to silicon ('Si) substrates conventionally used in semiconductor manufacturing, materials that satisfy the above requirements include boron nitride (BN), boron carbide (B, C), and boron silicide (B4S).
In recent years, mask substrates for X-ray lithography using boride such as
No. Specification).
これら硼化物のうち、特に窒化硼素は前記（２）、（６
）の条件を除けばその他の条件をほぼ満足するため、Ｘ
線リソグラフィ用のマスク基板として好適な材料である
といえる。Among these borides, boron nitride is particularly used in (2) and (6) above.
), since most of the other conditions are satisfied, except for the condition
It can be said that this material is suitable as a mask substrate for line lithography.
この、Ｘ線リソグラフィ用の窒化硼素膜を製造する方法
としては、硼素のハロゲン化物（ＢＣｌ２、ＢＰ、、Ｂ
Ｂｒ＋等）あるいはジボラン（ＢｔＨｅ ）とアンモニ
ア（ＮＨ，）とを用いて、４００℃〜７００℃程度の温
度において、化学気相堆積（ＣＶＤ）法により基板上に
薄膜状に堆積さＵｏで作製する方法が一般的である。As a method for manufacturing this boron nitride film for X-ray lithography, boron halides (BCl2, BP, B
Br+ etc.) or diborane (BtHe) and ammonia (NH,) are deposited in a thin film on a substrate by chemical vapor deposition (CVD) at a temperature of about 400°C to 700°C. The method is common.
「発明が解決しようとする問題点」
ところで、前述の窒化硼素膜をＸ線リソグラフィ用の基
板として使用する際に遺されていた問題としては、形成
された膜に平坦性を持たせるために、この膜に適当な引
張応力を与えることがあった。"Problems to be Solved by the Invention" By the way, there are problems that remain when using the aforementioned boron nitride film as a substrate for X-ray lithography, in order to give the formed film flatness. Appropriate tensile stress could be applied to this membrane.
しかし、前記形成された膜に対する応力の付与は、成膜
温度、ガス圧、ｎＦパワー等により従来制御されてきた
が、窒化硼素膜に応力を与える要因についてはまだ十分
に解明されているとは言えず、従って、前述の如くＸ線
リソグラフィ用として供用しうる程度の平坦さを有する
窒化硼素膜の提供は困難な状況にあった。However, although the application of stress to the formed film has conventionally been controlled by the film formation temperature, gas pressure, nF power, etc., the factors that apply stress to the boron nitride film are still not fully understood. Therefore, as mentioned above, it has been difficult to provide a boron nitride film that is flat enough to be used for X-ray lithography.
この発明は前記問題点に鑑みてなされたもので、その目
的とするところは、Ｘ線リソグラフィ用マスク基板とし
て十分な平坦さを有する窒化硼素膜を製造することの可
能な、六方晶窒化硼素膜の応力制御方法を提供すること
にある。This invention has been made in view of the above problems, and its purpose is to provide a hexagonal boron nitride film that can produce a boron nitride film having sufficient flatness as a mask substrate for X-ray lithography. The object of the present invention is to provide a stress control method.
「問題点を解決するための手段」
前記問題点を解決するために、この発明のうち第１の発
明は、窒素化合物と硼素化合物とを化学気相堆積（ＣＶ
Ｄ）法により反応させることで、六方晶窒化硼素膜を基
板上に堆積させる際に、この基板に六方晶窒化硼素より
も熱膨張係数の低い基板を用いると共に、前記反応後に
窒化硼素膜が室温に冷却される際に、この窒化硼素膜に
作用する収縮力を前記基板が緩和することで、室温時に
窒化硼素膜全体に均一な引張応力が作用するように、前
記基板の板厚を決定するような六方晶窒化硼素膜の応力
制御方法を構成している。"Means for Solving the Problems" In order to solve the problems mentioned above, the first invention of the present invention is to deposit a nitrogen compound and a boron compound by chemical vapor deposition (CVV).
D) When a hexagonal boron nitride film is deposited on a substrate by the reaction method, a substrate with a thermal expansion coefficient lower than that of hexagonal boron nitride is used, and the boron nitride film is kept at room temperature after the reaction. The thickness of the substrate is determined so that a uniform tensile stress is applied to the entire boron nitride film at room temperature by relaxing the shrinkage force that acts on the boron nitride film when the boron nitride film is cooled. This method constitutes a stress control method for a hexagonal boron nitride film.
また、第２の発明は、前記第１の発明と同様に、窒化硼
素を堆積させる基板に六方晶窒化硼素よりも熱膨張係数
の低い基板を用いると共に、窒化硼素膜堆積前に、その
熱膨張係数が基板及び窒化硼素の中間にある緩衝層を前
記基板上に形成するような六方晶窒化硼素膜の応力制御
方法を構成している。Further, in a second invention, similar to the first invention, a substrate having a thermal expansion coefficient lower than that of hexagonal boron nitride is used as the substrate on which boron nitride is deposited, and the thermal expansion coefficient is adjusted before depositing the boron nitride film. A method for controlling stress in a hexagonal boron nitride film is constructed in which a buffer layer having a coefficient intermediate between that of the substrate and boron nitride is formed on the substrate.
さらに、第３の発明は、前記第！及び第２の発明と同様
に、窒化硼素を堆積させろ基板に六方晶窒化硼素よりも
熱膨張係数の低い基板を用い名と共に、前記基板の結晶
方向を乱雑にさせることで、基板上に堆積される窒化硼
素を微結晶化するような六方晶窒化硼素膜の応力制御方
法を構成している。Furthermore, the third invention is the above-mentioned! Similarly to the second invention, boron nitride is deposited on the substrate by using a substrate with a lower coefficient of thermal expansion than hexagonal boron nitride, and by arranging the crystal orientation of the substrate. This method constitutes a stress control method for a hexagonal boron nitride film that microcrystallizes boron nitride.
以下、この発明の六方晶窒化硼素膜の応力制御方法につ
いて、第１図ないし第５図を参照して、工程を追って詳
細に説明する。Hereinafter, the stress control method for a hexagonal boron nitride film according to the present invention will be explained in detail step by step with reference to FIGS. 1 to 5.
第１図は、この発明に従って製造された六方晶窒化硼素
膜を示す図である。図中、符号ｌは六方晶窒化硼素膜で
あり、この六方晶窒化硼素膜ｌの周縁部は、枠体に形成
された石英ガラス等の基板２により支持され、その平坦
性が維持されている。FIG. 1 is a diagram showing a hexagonal boron nitride film manufactured according to the present invention. In the figure, reference numeral 1 denotes a hexagonal boron nitride film, and the peripheral edge of this hexagonal boron nitride film 1 is supported by a substrate 2 made of quartz glass or the like formed on a frame to maintain its flatness. .
この発明に係わる六方晶窒化硼素膜！製造に使用される
前記窒素化合物としては、アンモニア（ＮＨ３）、ヒド
ラジン（Ｎ２Ｈ，）、トリアルキルアミン（Ｎ（ＣｎＨ
ｔｎ＋＋ ）ｓ ）等が挙げられるが、取り扱い上の点
でアンモニアが好ましい。Hexagonal boron nitride film according to this invention! The nitrogen compounds used in the production include ammonia (NH3), hydrazine (N2H,), trialkylamine (N(CnH,)
tn++)s), etc., but ammonia is preferred from the viewpoint of handling.
また、前記硼素化合物としては、硼素のハロゲン化物（
ＢＣＩ、ｌ、ＢＦａ、ＢＢｒ３等）、ジボラン（ＩＩＨ
＠ ）、トリエチルボラン＜ Ｂ（ＣｔＨｓ）ｓ ）、
あるいはトリメトキシボリン（Ｂ （Ｃｔｌ ３０ ）
３ ）等が挙げられるが、取り扱い上の点でトリメトキ
シボリンが最も好ましく、この場合、担体ガスとしては
水素あるいは窒素を用いれば良い。Further, as the boron compound, boron halide (
BCI, l, BFa, BBr3, etc.), diborane (IIH
@), triethylborane < B(CtHs)s),
Or trimethoxyborine (B (Ctl 30 )
3), etc., but trimethoxyborine is most preferred from the viewpoint of handling, and in this case, hydrogen or nitrogen may be used as the carrier gas.
これら窒素化合物及び硼素化合物を用いて、化学気相堆
積（以下、ＣＶＤと称する）法により、第１図に示すよ
うな六方晶窒化硼素膜ｌを作製するわけだが、前記ＣＶ
Ｄ法を実現するためのＣＶＤ装置は、常圧ＣＶＤ装置、
減圧ＣＶＤ装置等周知の装置で良く、同等特殊な手段、
装置を必要としない。また、前記硼素化合物にトリエチ
ルボラン、トリメトキシボリン等の有機金属を使用した
場合、いわゆる有機金属熱分解化学気相堆積（ＭＯＣＶ
Ｄ ）法と呼ばれる手法を用いて、窒素化合物及び硼素
化合物（有機金属）の反応により六方晶窒化硼素膜１を
作製することになるが、この場合においても、従来使用
されているＭＯＣＶＤ装置を用いれば良い。なお、基板
２上に堆積される六方晶窒化硼素膜１の膜厚は、その使
用用途により適宜決定されれば良いが、０，５〜５０μ
ｍ程度が好ましい。Using these nitrogen compounds and boron compounds, a hexagonal boron nitride film l as shown in FIG. 1 is produced by chemical vapor deposition (hereinafter referred to as CVD).
The CVD equipment for realizing method D is a normal pressure CVD equipment,
Well-known devices such as low-pressure CVD devices may be used, and equivalent special means,
No equipment required. In addition, when an organic metal such as triethylborane or trimethoxyborine is used as the boron compound, so-called metal organic pyrolysis chemical vapor deposition (MOCV)
The hexagonal boron nitride film 1 will be produced by the reaction of a nitrogen compound and a boron compound (organic metal) using a method called D) method, but in this case as well, a conventionally used MOCVD apparatus can be used. Good. The thickness of the hexagonal boron nitride film 1 deposited on the substrate 2 may be determined as appropriate depending on its intended use, but may range from 0.5 to 50 μm.
About m is preferable.
前記窒素化合物及び硼素化合物を７００°Ｃ−１７００
℃、好ましくは９０．０°Ｃ〜１１００℃の範囲内の温
度で反応さＵ・、基板２上に六方晶窒化硼素膜ｌを堆積
させろことが好ましい。すなわち、７００℃より低い温
度での反応では、曲述の如く基板２上に堆積される窒化
硼素が十分に結晶化されないと共に、前記硼素化合物の
担体ガスとして使用される水素１−１ 、等の混入を招
くこととなり、さらに言えば、その堆積速度が遅く、不
経済である。また、１７００℃より高い温度での反応で
は、原料化合物がＣＶＤ装置の反応管の表面で分解され
てしまい、前記基板２上への堆積速度が低下するため、
不経済となる。The nitrogen compound and boron compound were heated at 700°C-1700°C.
It is preferred to deposit the hexagonal boron nitride film on the substrate 2 by reacting at a temperature in the range of 90.0°C to 1100°C. That is, in a reaction at a temperature lower than 700°C, the boron nitride deposited on the substrate 2 is not sufficiently crystallized as described above, and hydrogen 1-1, etc. used as a carrier gas for the boron compound is Furthermore, the rate of deposition is slow and uneconomical. In addition, in a reaction at a temperature higher than 1700° C., the raw material compound is decomposed on the surface of the reaction tube of the CVD apparatus, and the deposition rate on the substrate 2 is reduced.
It becomes uneconomical.
前記ＣＶＤ装置の反応管へ流入させる窒素化合物及び硼
素化合物の流入速度は、−例として窒素化合物にアンモ
ニア、また硼素化合物にトリエチルボランを使用した場
合、そのモル比でＮＨｓ／Ｂ（Ｃ２Ｈ４）３≧２５であ
れば、基板２上にほぼ化学量論組成の窒化硼素膜１が堆
積されろ。逆に、前記モル比が２５未満であると、基板
２上に堆積される窒化硼素中の窒素／硼素成分比Ｎ／［
３が１より大きく低下してしまう。また、前記温度範囲
内であれば、その成分比Ｎ／Ｂがほぼｌに近いような窒
化硼素膜を作製することができる。The inflow rate of the nitrogen compound and boron compound into the reaction tube of the CVD apparatus is - For example, when ammonia is used as the nitrogen compound and triethylborane is used as the boron compound, the molar ratio is NHs/B(C2H4)3≧ 25, a substantially stoichiometric boron nitride film 1 is deposited on the substrate 2. Conversely, if the molar ratio is less than 25, the nitrogen/boron component ratio N/[ in the boron nitride deposited on the substrate 2
3 becomes much lower than 1. Further, within the temperature range described above, a boron nitride film whose component ratio N/B is close to l can be produced.
前記ＣＶＤ装置の反応管内に配置され、その上面に窒化
硼素膜が堆積されろ基板２としては、第２図に示すよう
に、その板厚が０．３〜２．０ｍｍ程度の石英ガラス板
、酸化アルミニウム（サファイヤ）板、あるいはシリコ
ン基板等が挙げられるが、前記高温での反応後に、室温
に戻した状態で前記窒化硼素膜に適当な引張応力を与え
るために、窒化硼素の熱膨張係数（ＩＸＩＯ−”）より
低い熱膨張係数を有する石英ガラス（熱膨張係数５ＸＩ
Ｏ−７）基板が好ｊしい。As shown in FIG. 2, the substrate 2 placed in the reaction tube of the CVD apparatus and on which the boron nitride film is deposited is a quartz glass plate having a thickness of about 0.3 to 2.0 mm; Aluminum oxide (sapphire) plates, silicon substrates, etc. may be used, but the thermal expansion coefficient ( quartz glass with a lower coefficient of thermal expansion (coefficient of thermal expansion 5XI
O-7) Substrate is preferred.
ここで、この基板２の板厚を前記熱膨張係数の差によっ
て適宜調整すれば、温度低下に伴う収縮により窒化硼素
膜に作用される応力を調節し、これにより室温に戻した
状態で窒化硼素膜に適度な張力が加えられろようにする
ことができる。ずなわち、基板２に石英ガラス基板等熱
膨張係数の低い基板を使用した場合、基板２の板厚が薄
ければ、室温に戻した状態でこの基板が大きく湾曲し、
逆に基板２の板厚が厚ければ、前記湾曲の度合も小さい
からである。Here, if the thickness of the substrate 2 is adjusted appropriately according to the difference in the thermal expansion coefficient, the stress applied to the boron nitride film due to shrinkage due to temperature drop can be adjusted, and thereby the boron nitride film can be heated to room temperature. Appropriate tension can be applied to the membrane. In other words, if a substrate with a low coefficient of thermal expansion, such as a quartz glass substrate, is used as the substrate 2, and the thickness of the substrate 2 is thin, the substrate will curve significantly when returned to room temperature.
Conversely, if the thickness of the substrate 2 is thicker, the degree of curvature will be smaller.
また、前記石英ガラス基板でも窒化硼素との熱膨張係数
の差が大きいので、基板２上に予め窒化硼素に比較的熱
膨張係数の近い物質からなる緩衝層を形成しておくのが
好ましい。この緩衝層としては、前記石英ガラスと同一
の材料である二酸化珪素（ＳｉＯりを、蒸着法あるいは
スパッタリング法により、厚さ０．２μ肩〜ｌμ度の範
囲で、基板２上面に形成したような緩衝層が挙げられる
。Further, since the quartz glass substrate also has a large difference in coefficient of thermal expansion from boron nitride, it is preferable to form a buffer layer on the substrate 2 in advance, which is made of a material whose coefficient of thermal expansion is relatively similar to that of boron nitride. As this buffer layer, silicon dioxide (SiO), which is the same material as the silica glass, is formed on the upper surface of the substrate 2 to a thickness of 0.2 μm to 1 μm by vapor deposition or sputtering. Examples include a buffer layer.
この場合、蒸着あるいはスパッタリングの速度をｌＯ〜
ｌＯＯ人／秒と通常よりも速くすることで、所望の熱膨
張係数を有する緩衝層を得ることができる。In this case, the rate of vapor deposition or sputtering is
A buffer layer having a desired coefficient of thermal expansion can be obtained by increasing the speed to 100 people/second, which is faster than usual.
さらに、六方晶窒化硼素は、硼素と窒素が交互に結合し
てベンゼンと同様なボラジン環を形成したものが２次元
に連なり、これがファンデルワールス力によって重積さ
れたものと考えられており、従って、このボラジン環に
平行な方向（ａ軸方向）の熱膨張係数（ｌＸｌ０″″５
）と、ボラジン環に直交する方向（Ｃ軸方向）の熱膨張
係数（４×ｌＯ′″＠）とが大きく異なる、゛という性
質を有している。ここで、本発明者の研究結果によれば
、この発明に係わる六方晶窒化硼素膜ｌの製造方法によ
って製造された六方晶窒化硼素膜１の結晶方向は、基板
またる石英ガラス等の窒化硼素膜ｌ堆積面における構造
状態に左右され、いわゆる基゛板２側の［結合の手」に
連なる方向で窒化硼素の結晶が成長ずろことが明らかに
なっている。従って、この基板２の構造状態を適宜制御
することによって、六方晶窒化硼素膜ｌの結晶状態をも
制御することが可能であると共に、その熱膨張係数ら、
前記石英ガラスの熱膨張係数により近付いた、所望の熱
膨張係数に制御することが可能となる。Furthermore, hexagonal boron nitride is thought to be a two-dimensional chain of boron and nitrogen atoms bonded alternately to form borazine rings similar to benzene, which are stacked together by van der Waals forces. Therefore, the coefficient of thermal expansion in the direction parallel to this borazine ring (a-axis direction) (lXl0''''5
) and the coefficient of thermal expansion (4×lO′″@) in the direction perpendicular to the borazine ring (C-axis direction) are significantly different.Here, based on the research results of the present inventors, According to the invention, the crystal orientation of the hexagonal boron nitride film 1 produced by the method for producing a hexagonal boron nitride film 1 according to the present invention depends on the structural state of the boron nitride film 1 deposited surface of quartz glass or the like that spans the substrate. It has been revealed that boron nitride crystals grow in the direction of the so-called bonding hands on the substrate 2 side. Therefore, by appropriately controlling the structural state of this substrate 2, it is possible to control the crystal state of the hexagonal boron nitride film l, and also to control its thermal expansion coefficient, etc.
It becomes possible to control the thermal expansion coefficient to a desired value closer to that of the quartz glass.
以上述べた方法により、第３図に示すような、基板２上
に結晶化された六方晶窒化硼素膜ｌを作製することがで
きろ。この後、前述の如くＸ線゛リソグラフィ用のマス
ク基板として供用されるためには、前記石英ガラス等の
基板２の一部あるいは全体を除去して膜単体にする必要
がある。この際、前記六方晶窒化硼素膜ｌは、いわゆる
耐熱性セラミックスの一種であるため、エツチング液に
対する耐性が良好であり、その特性変化等に細心の注意
を払う必要がない。以下、この手順を工程を追って説明
する。By the method described above, it is possible to produce a crystallized hexagonal boron nitride film l on the substrate 2 as shown in FIG. Thereafter, in order to use the substrate 2 as a mask substrate for X-ray lithography as described above, it is necessary to remove a portion or the entirety of the substrate 2 made of quartz glass or the like to form a single film. At this time, since the hexagonal boron nitride film 1 is a type of so-called heat-resistant ceramics, it has good resistance to etching solutions, and there is no need to pay close attention to changes in its characteristics. This procedure will be explained step by step below.
まず、第３図に示すような、基板２上に堆積した六方晶
窒化硼素膜ｌに、第４図に示すように、その上面、側面
、及び基板２下面の周縁部等残存すべき個所にエツチン
グ液が触れないようにワックス３を塗布する。このワッ
クス３は、従来半導体製造工程で慣用されているワック
スで良く、同等特殊な性質の乙のが要求されることはな
い。次に、前記基板２のけ質に対応するエツチング液（
例えば基板２に石英ガラスを使用した場合には弗酸（Ｈ
Ｆ）からなるエツチング、＆）により、この基板２を、
第５図に示すように、その周縁部のみを残して除去する
。この後、ワックス３を除去すれば、第１図に示すよう
な六方晶窒化硼素膜１を得ることができる。First, the hexagonal boron nitride film l deposited on the substrate 2 as shown in FIG. Apply wax 3 so that the etching solution does not touch it. The wax 3 may be a wax that has been conventionally used in semiconductor manufacturing processes, and does not require wax having similar special properties. Next, an etching solution (
For example, when quartz glass is used for the substrate 2, hydrofluoric acid (H
By etching consisting of F) and &), this substrate 2 is
As shown in FIG. 5, it is removed leaving only the peripheral edge. Thereafter, by removing the wax 3, a hexagonal boron nitride film 1 as shown in FIG. 1 can be obtained.
以上説明した六方晶窒化硼素膜！の応力制御方法は、窒
化硼素が堆積される基板２の板厚を制御したり、基ＶＸ
、２と窒化硼素膜ｌとの間に緩衝層を設けたり、堆積さ
れる窒化硼素膜ｌを微結晶化することを特徴とするもの
であるから、この応力制御方法によれば、室温に戻った
状態でこの六方晶窒化硼素膜ｉに適当な引張応力を与え
ることができる。よって、この応力制御方法によれば、
Ｘ線リソグラフィ用マスク基板として十分な平坦さを有
ずろ窒化硼素膜を製造することの可能な、六方晶窒化硼
素膜の応力制御方法を実現することができる。The hexagonal boron nitride film explained above! The stress control method includes controlling the thickness of the substrate 2 on which boron nitride is deposited, and
, 2 and the boron nitride film l, and the deposited boron nitride film l is microcrystallized. In this state, an appropriate tensile stress can be applied to this hexagonal boron nitride film i. Therefore, according to this stress control method,
It is possible to realize a method for controlling stress in a hexagonal boron nitride film that can produce a zero boron nitride film having sufficient flatness as a mask substrate for X-ray lithography.
この発明に係わる六方晶窒化硼素膜の応力制御方法によ
って製造された六方晶窒化硼素膜ｌは、前記の如くＸ線
リソグラフィのマスク基板に用いられるだけでなく、電
子回路、音響素子等の薄膜基板にも好適に用いられる。The hexagonal boron nitride film l produced by the hexagonal boron nitride film stress control method according to the present invention is not only used as a mask substrate for X-ray lithography as described above, but also as a thin film substrate for electronic circuits, acoustic elements, etc. It is also suitably used.
「実施例」
以下、この発明の六方晶窒化硼素膜の応力制御方法を、
実施例により更に詳細に説明するが、この発明の応力制
御方法は、以下に示す実施例に限定されない。"Example" Hereinafter, the method for controlling stress in a hexagonal boron nitride film of the present invention will be described.
The stress control method of the present invention will be explained in more detail with reference to Examples, but the stress control method of the present invention is not limited to the Examples shown below.
（実験例）
全長６００■、内径２５１１φの石英ガラス製の反応器
中に、トリエチルボラン（以下、ＴＥＢと略称する、純
度９８％）、アンモニア（純度９９゜９％）、水素（純
度９９．９９９％）及びアルゴン（純度９９．９９５％
）を流入させて、ＭＯＣＶＤ法により六方晶窒化硼素膜
を製作した。窒化硼素膜が堆積される基板としては、酸
化アルミニウム板（サファイヤ、寸法１２Ｘ１２Ｘ０．
６ＪＩＪＩ３ ）及びシリコン基板（寸法１２ｘ１２ｘ
Ｏ，２５ｍ！３ ）を使用した。これら基板は、焼結形
成された窒化硼素膜の基板ホルダ上に水平方向から２０
度傾斜させて載置、固定し、外部に設置した炉により所
定の温度に加熱した。基板周辺の温度は、前記反応器内
に挿入した熱電対により測定した。(Experiment example) Triethylborane (hereinafter abbreviated as TEB, purity 98%), ammonia (purity 99°9%), hydrogen (purity 99.999 %) and argon (purity 99.995%
) to produce a hexagonal boron nitride film by the MOCVD method. The substrate on which the boron nitride film is deposited is an aluminum oxide plate (sapphire, dimensions 12X12X0.
6JIJI3) and silicon substrate (dimensions 12x12x
O, 25m! 3) was used. These substrates are placed on a sintered boron nitride film substrate holder from a horizontal direction.
It was placed and fixed at an angle of 100 degrees, and heated to a predetermined temperature in an external furnace. The temperature around the substrate was measured with a thermocouple inserted into the reactor.
ＴＥＢは、このＴＥＢ中に水素ガスをバブリングするこ
とで搬送した。また、このＴＥＢ飽和器の温度は、θ℃
〜２５℃の間で選び一定に維持した。ＴＥ［３の流量は
、この’Ｉ’ Ｅ Ｂ飽和器からのＴＥｎ損失量から算
出した。この実験例の他の実験条件については、第１表
に示す通りである。The TEB was transported by bubbling hydrogen gas into the TEB. Also, the temperature of this TEB saturator is θ℃
The temperature was chosen and kept constant between ~25°C. The flow rate of TE[3 was calculated from the amount of TEn loss from this 'I' E B saturator. Other experimental conditions for this experimental example are as shown in Table 1.
第 １ 表
以上述べた方法により基板上に堆積された薄膜を、Ｘ線
回折により分析したところ、（００２）方向のみに強い
ピークを検出した。これは、ＪＷ仮而面対して垂直方向
に結晶軸のＣ軸が配向された状態で、結晶が堆積された
ことを示し、これにより基板上に堆積された薄膜が六方
晶の結晶構造を有す、ることか判明した。Table 1 When the thin film deposited on the substrate by the method described above was analyzed by X-ray diffraction, a strong peak was detected only in the (002) direction. This indicates that the crystal was deposited with the C axis of the crystal axis perpendicular to the JW metaplane, and as a result, the thin film deposited on the substrate had a hexagonal crystal structure. Well, it turned out to be true.
次に、前記Ｘ線回折データから格子定数ＣＯ（入）を算
出し、この格子定数００を縦軸に、また堆積温度（’Ｃ
）を横軸に取った場合の、格子定数Ｃ０と堆積温度との
関係を、第６図に示す。温度の上昇に従って、格子定数
Ｇｏが小さくなり、バルクの状態で得られろ窒化硼素結
晶の格子定数６．６６人に漸近することが判る。すなわ
ち、堆積温度の上昇に従って、基板上に堆積される窒化
硼素膜の結晶化がより完全になるのである。またこれは
、前記Ｘ線回折におけるピークの半値幅が、温度上昇に
従って狭くなるという実験結果からも裏付けられた。Next, the lattice constant CO (in) is calculated from the X-ray diffraction data, and the vertical axis is the lattice constant 00, and the deposition temperature ('C
) is plotted on the horizontal axis, and the relationship between the lattice constant C0 and the deposition temperature is shown in FIG. It can be seen that as the temperature rises, the lattice constant Go becomes smaller and approaches asymptotically to the lattice constant of 6.66 of the boron nitride crystal obtained in the bulk state. That is, as the deposition temperature increases, the crystallization of the boron nitride film deposited on the substrate becomes more complete. This was also supported by the experimental result that the half-width of the peak in the X-ray diffraction narrows as the temperature rises.
また、前記Ｘ線回折のピーク強度から、基板上への薄膜
堆積速度を算出し、この堆積速度の対数を縦軸に、また
絶対反応温度の逆数を横軸にしてグラフ化した実験結果
を、第７図に示す。なお、この時、ＴＥＢとアンモニア
のモル比Ｎ Ｈ２／ Ｂ（ＣｔＨ６）、＝ ３０ で
一定であった。図示の如く、温度７５０℃において堆積
速度は０．０２５μＲ（２，５ｘｌＯ”人）７秒であっ
たのが、１０００℃において０，９６μＮ（９，６Ｘ１
０’入）７秒と上昇する。In addition, the experimental results were obtained by calculating the thin film deposition rate on the substrate from the peak intensity of the X-ray diffraction, and graphing the logarithm of this deposition rate on the vertical axis and the reciprocal of the absolute reaction temperature on the horizontal axis. It is shown in FIG. At this time, the molar ratio of TEB to ammonia, N H2/B(CtH6), was constant at 30. As shown in the figure, the deposition rate was 0.025 μR (2,5×1 O” person) 7 seconds at a temperature of 750°C, but it was 0.96 μN (9,6×1 O” person) at 1000°C.
0' entered) increases to 7 seconds.
さらに、前記基板上に堆積された窒化硼素膜からの蛍光
Ｘ線を微小点Ｘ線分析器により測定し、窒化硼素中の窒
素成分による硼素にα、線のシフト量からこの窒化硼素
膜の成分を測定した。この測定結果から得られる窒素及
び硼素の成分比Ｎ／Ｂを縦軸に、また、ＴＥＢとアンモ
ニアとのモル比Ｎ Ｈｓ／ ［３（Ｃｔｌ−Ｉ Ｓ）３
を横軸に取ってグラフ化した実験結果を第８図に示す。Furthermore, fluorescent X-rays from the boron nitride film deposited on the substrate are measured using a micropoint X-ray analyzer, and the amount of shift of the line is determined by the shift amount of the boron due to the nitrogen component in the boron nitride. was measured. The component ratio N/B of nitrogen and boron obtained from this measurement result is plotted on the vertical axis, and the molar ratio of TEB and ammonia N Hs/[3(Ctl-IS)3
The experimental results are shown in FIG. 8, graphed on the horizontal axis.
なお、この時の温度＋、ｔ ｔ ｏ ｏ ｏ℃、ＴＥＢ
の流！！ｌＯ，８３１１２／分、全体の流量は１３０ス
Ｑ／分であり、前記各窒素及び硼素の成分量は、標準の
窒化硼素試料により補正した。第８図に示すように、前
記モル比が２５以上であれば、は“ぼ化学量論的に完全
な窒化硼素膜を基板上に堆積させることが可能である。In addition, the temperature at this time +, t t o o o ℃, TEB
The flow! ! The total flow rate was 130 sQ/min, and the amounts of nitrogen and boron were corrected using standard boron nitride samples. As shown in FIG. 8, if the molar ratio is 25 or more, it is possible to deposit a nearly stoichiometrically perfect boron nitride film on the substrate.
すなわち、前記モル比が２５以上であるように前記Ｔ
ＥＢ及びアンモニアを流入させれば、はぼ純粋の窒化硼
素膜が得られることが、前記実験結果から理解できる。That is, the T
It can be understood from the above experimental results that a substantially pure boron nitride film can be obtained by flowing EB and ammonia.
また、前記窒素及び硼素の成分比を縦軸に、堆積温度を
横軸に取ってグラフ化した実験結果を第９図に示す。な
お、この時のＴＥＢとアンモニアとのモル比Ｎ Ｈ３／
Ｂ （ＣｙＨｓＬは、１０及び３０の２種類に設定し
た。第９図に見る如く、前記成分比は、面記第７図と同
様に、Ｉ ０００℃付近の堆積温度においてピークを迎
えている。つまり、第７図及び第９図の結果から、１０
００℃付近、すなわち９００℃〜！Ｉ００℃の範囲内で
の窒化硼素膜の作製が、最も効率が良いことが理解でき
る。Further, FIG. 9 shows the experimental results, which are graphed with the nitrogen and boron component ratios plotted on the vertical axis and the deposition temperature plotted on the horizontal axis. In addition, the molar ratio of TEB and ammonia at this time is NH3/
B (CyHsL was set to two types, 10 and 30. As seen in FIG. 9, the component ratio reaches its peak at a deposition temperature around I 000° C., as in FIG. 7. In other words, from the results shown in Figures 7 and 9, 10
Around 00℃, that is, 900℃ ~! It can be seen that manufacturing the boron nitride film within the range of I00° C. is most efficient.
最後に、酸化アルミニウム板上に堆積された窒化硼素膜
の波長２．５μｍ１〜５０μＲ（波数４０００ ｃｍ−
’ 〜２００ ｃｍ−’ ）における赤外線反射（図中
破線）及び透過（図中実線）スペクトルを、第１θ図に
示す。ここで、反射率及び透過率のリファレンスとして
は、アルミニウム蒸着膜及び無表面加工のシリコン基板
を用いた。図中、波数１６００ ＣＩ−’ 〜ｌ ３０
０ Ｃ１ｌ！−’に相当する吸収帯は、窒化硼素の市内
振動を示すものであり、これによってら基板上に純粋の
窒化硼素膜が形成されていることが理解できる。Finally, the wavelength of the boron nitride film deposited on the aluminum oxide plate was 2.5 μm1~50 μR (wave number 4000 cm−
The infrared reflection (dashed line in the figure) and transmission (solid line in the figure) spectra at 200 cm-' are shown in Fig. 1θ. Here, as a reference for reflectance and transmittance, an aluminum vapor-deposited film and a silicon substrate with no surface processing were used. In the figure, wave number 1600 CI-' ~ l 30
0 C1l! The absorption band corresponding to -' indicates the internal vibration of boron nitride, and it can be understood from this that a pure boron nitride film is formed on the substrate.
「発明の効果」
以上詳細に説明したように、この発明は、窒化硼素が堆
積される基板の板厚を制御したり、基板と窒化硼素膜と
の間に緩衝層を設けたり、堆積される窒化硼素膜を微結
晶化することを特徴とするものであるから、この応力制
御方法によれば、室温に戻った状態でこの六方晶窒化硼
素膜に適当な引張応力を与えることができる。よって、
この応力制御方法によれば、Ｘ線リソグラフィ用マスク
基板として十分な平坦さを有する窒化硼素膜を製造する
ことの可能な、六方晶窒化硼素膜の応力制御方法を実現
することができろ。"Effects of the Invention" As explained in detail above, the present invention can control the thickness of the substrate on which boron nitride is deposited, provide a buffer layer between the substrate and the boron nitride film, and Since the method is characterized in that the boron nitride film is microcrystallized, according to this stress control method, an appropriate tensile stress can be applied to the hexagonal boron nitride film when the temperature returns to room temperature. Therefore,
According to this stress control method, it is possible to realize a stress control method for a hexagonal boron nitride film that can produce a boron nitride film having sufficient flatness as a mask substrate for X-ray lithography.
第１図はこの発明に係わる六方品窒化硼素膜の応力制御
方法に従って製造された六方晶窒化硼素膜を示す模式図
、第２図ないし第５図は、六方晶窒化硼素膜の製造方法
を説明するための工程図、第６図は格子定数と堆積温度
との関係を示す図、第７図は堆積速度と絶対反応温度と
の関係を示す図、第８図は窒素及び硼素の成分比とアン
モニア及びトリエヂルボロンのモル比との関係を示す図
、第９図は窒素及び硼素の成分比と堆積温度との関係を
示す図、第１Ｏ図は窒化硼素膜の赤外線反射支び透過ス
ペクトルを示す図である。
ｌ・・・・・・六方晶窒化硼素膜、２・・・・・・基板
。
出願人 中 村 勝 光日本酸素株式会
社
区
憾
吊 ａ Ｑ）（０
埃＋板馨（Ｏく］
区
ト
城
貨驚釉徳（・＜・Ｓ−１）FIG. 1 is a schematic diagram showing a hexagonal boron nitride film manufactured according to the stress control method for a hexagonal boron nitride film according to the present invention, and FIGS. 2 to 5 illustrate a method for manufacturing a hexagonal boron nitride film. Figure 6 is a diagram showing the relationship between lattice constant and deposition temperature, Figure 7 is a diagram showing the relationship between deposition rate and absolute reaction temperature, and Figure 8 is a diagram showing the relationship between nitrogen and boron component ratios. Figure 9 shows the relationship between the molar ratio of ammonia and triedylboron, Figure 9 shows the relationship between the component ratio of nitrogen and boron and deposition temperature, and Figure 1O shows the infrared reflection and transmission spectrum of a boron nitride film. It is. 1...Hexagonal boron nitride film, 2...Substrate. Applicant: Masaru Nakamura Nippon Sanso Co., Ltd. A Q)
Claims (3)
Ｄ）法により反応させることで、六方晶窒化硼素膜を基
板上に堆積させる際に、この基板に六方晶窒化硼素より
も熱膨張係数の低い基板を用いると共に、前記反応後に
窒化硼素膜が室温に冷却される際に、この窒化硼素膜に
作用する収縮力を前記基板が緩和することで、室温時に
窒化硼素膜全体に均一な引張応力が作用するように、前
記基板の板厚を決定することを特徴とする六方晶窒化硼
素膜の応力制御方法。(1) Chemical vapor deposition (CV) of nitrogen compounds and boron compounds
D) When a hexagonal boron nitride film is deposited on a substrate by the reaction method, a substrate with a thermal expansion coefficient lower than that of hexagonal boron nitride is used, and the boron nitride film is kept at room temperature after the reaction. The thickness of the substrate is determined so that a uniform tensile stress is applied to the entire boron nitride film at room temperature by relaxing the shrinkage force that acts on the boron nitride film when the boron nitride film is cooled. A method for controlling stress in a hexagonal boron nitride film, characterized by:
Ｄ）法により反応させることで、六方晶窒化硼素膜を基
板上に堆積させる際に、この基板に六方晶窒化硼素より
も熱膨張係数の低い基板を用いると共に、前記窒化硼素
膜堆積前に、その熱膨張係数が基板及び窒化硼素の中間
にある緩衝層を前記基板上に形成することを特徴とする
六方晶窒化硼素膜の応力制御方法。(2) Chemical vapor deposition (CV) of nitrogen compounds and boron compounds
D) When depositing a hexagonal boron nitride film on a substrate by reacting with the method, a substrate having a lower coefficient of thermal expansion than hexagonal boron nitride is used, and before depositing the boron nitride film, 1. A method for controlling stress in a hexagonal boron nitride film, comprising forming on the substrate a buffer layer whose coefficient of thermal expansion is between that of the substrate and boron nitride.
Ｄ）法により反応させることで、六方晶窒化硼素膜を基
板上に堆積させる際に、この基板に六方晶窒化硼素より
も熱膨張係数の低い基板を用いると共に、前記基板の結
晶方向を乱雑にさせることで、基板上に堆積される窒化
硼素を微結晶化することを特徴とする六方晶窒化硼素膜
の応力制御方法。(3) Chemical vapor deposition (CV) of nitrogen compounds and boron compounds
D) When a hexagonal boron nitride film is deposited on a substrate by the reaction method, a substrate having a lower thermal expansion coefficient than hexagonal boron nitride is used, and the crystal orientation of the substrate is disordered. 1. A stress control method for a hexagonal boron nitride film, which comprises microcrystallizing boron nitride deposited on a substrate by microcrystallizing boron nitride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61292060A JPS63145779A (en) | 1986-12-08 | 1986-12-08 | Method for controlling stress of hexagonal boron nitride film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61292060A JPS63145779A (en) | 1986-12-08 | 1986-12-08 | Method for controlling stress of hexagonal boron nitride film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63145779A true JPS63145779A (en) | 1988-06-17 |
Family
ID=17777018
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61292060A Pending JPS63145779A (en) | 1986-12-08 | 1986-12-08 | Method for controlling stress of hexagonal boron nitride film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63145779A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010076955A (en) * | 2008-09-24 | 2010-04-08 | Mitsui Chemicals Inc | Sheet with metallic foil and laminated body for circuit board |
| CN103668106A (en) * | 2012-09-01 | 2014-03-26 | 董国材 | Method for preparing monolayer hexagonal boron nitride |
| JP2021020848A (en) * | 2016-05-12 | 2021-02-18 | グローバルウェーハズ カンパニー リミテッドＧｌｏｂａｌＷａｆｅｒｓ Ｃｏ．，Ｌｔｄ． | Direct formation of hexagonal boron nitride on silicon based dielectric |
-
1986
- 1986-12-08 JP JP61292060A patent/JPS63145779A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010076955A (en) * | 2008-09-24 | 2010-04-08 | Mitsui Chemicals Inc | Sheet with metallic foil and laminated body for circuit board |
| CN103668106A (en) * | 2012-09-01 | 2014-03-26 | 董国材 | Method for preparing monolayer hexagonal boron nitride |
| CN103668106B (en) * | 2012-09-01 | 2016-01-20 | 董国材 | A kind of method preparing monolayer hexagonal boron nitride |
| JP2021020848A (en) * | 2016-05-12 | 2021-02-18 | グローバルウェーハズ カンパニー リミテッドＧｌｏｂａｌＷａｆｅｒｓ Ｃｏ．，Ｌｔｄ． | Direct formation of hexagonal boron nitride on silicon based dielectric |
| US11276759B2 (en) | 2016-05-12 | 2022-03-15 | Globalwafers Co., Ltd. | Direct formation of hexagonal boron nitride on silicon based dielectrics |
| US11289577B2 (en) | 2016-05-12 | 2022-03-29 | Globalwafers Co., Ltd. | Direct formation of hexagonal boron nitride on silicon based dielectrics |
| JP2022121422A (en) * | 2016-05-12 | 2022-08-19 | グローバルウェーハズ カンパニー リミテッド | Direct formation of hexagonal boron nitride on silicon based dielectrics |
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