JPH0371398B2 - - Google Patents

Info

Publication number
JPH0371398B2
JPH0371398B2 JP59099463A JP9946384A JPH0371398B2 JP H0371398 B2 JPH0371398 B2 JP H0371398B2 JP 59099463 A JP59099463 A JP 59099463A JP 9946384 A JP9946384 A JP 9946384A JP H0371398 B2 JPH0371398 B2 JP H0371398B2
Authority
JP
Japan
Prior art keywords
silicon
single crystal
wafer
silicon single
nitrogen
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
Application number
JP59099463A
Other languages
Japanese (ja)
Other versions
JPS60246297A (en
Inventor
Katsuhiko Miki
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shin Etsu Handotai Co Ltd
Original Assignee
Shin Etsu Handotai Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shin Etsu Handotai Co Ltd filed Critical Shin Etsu Handotai Co Ltd
Priority to JP9946384A priority Critical patent/JPS60246297A/en
Publication of JPS60246297A publication Critical patent/JPS60246297A/en
Publication of JPH0371398B2 publication Critical patent/JPH0371398B2/ja
Granted legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/02—Elements
    • C30B29/06—Silicon
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B23/00—Single-crystal growth by condensing evaporated or sublimed materials
    • C30B23/02—Epitaxial-layer growth

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Recrystallisation Techniques (AREA)

Description

【発明の詳細な説明】 産業上の利用分野 本発明は、気相エピタキシヤル成長によるシリ
コン単結晶の製造方法に関するもので、特に熱応
力に強い窒素ドープシリコン単結晶の製造方法に
係る。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for manufacturing silicon single crystals by vapor phase epitaxial growth, and in particular to a method for manufacturing nitrogen-doped silicon single crystals that are resistant to thermal stress.

従来の技術 近時半導体結晶のエピタキシヤルウエーハは、
LSI回路素子に幅広く利用されている。このウエ
ーハはLSI回路素子として加工される工程におい
て、酸化や拡散などの熱処理が行なわれるので、
この加熱にともなう熱応力によつてウエーハに転
位が発生し、ソリを生ずるようになる。このウエ
ーハに生ずるソリは回路形成の露光工程における
パターニングを不良にするので避けられる必要が
ある。Conventional technology Recently, epitaxial wafers of semiconductor crystals are
Widely used in LSI circuit elements. This wafer undergoes heat treatment such as oxidation and diffusion in the process of being processed into LSI circuit elements.
Thermal stress accompanying this heating causes dislocations to occur in the wafer, resulting in warpage. This warping that occurs on the wafer must be avoided because it causes poor patterning in the exposure process for circuit formation.

他方、溶融体からの引上げによるチヨクラルス
キー法によつて育成されるシリコン単結晶棒には
酸素が４×1017〜２×1018原子／cm3程度含有され
ており、この酸素の存在が熱応力に強く影響する
ことが知られている（S.M.Hu et al、Journal
of Applied Physics、46(5)、P.1869、1975）。こ
れは、含有酸素がシリコン単結晶中で転位の固着
作用をするためであると考えられる。 On the other hand, a silicon single crystal rod grown by the Czyochralski method by pulling from a melt contains about 4×10 17 to 2×10 18 atoms/cm 3 of oxygen, and the presence of this oxygen is It is known to strongly affect thermal stress (SMHu et al, Journal
of Applied Physics, 46 (5), P.1869, 1975). This is thought to be because the oxygen contained acts to fix dislocations in the silicon single crystal.

発明が解決しようとする問題点 上記公知の技術を応用し、シリコン単結晶のエ
ピタキシヤル成長において酸素を添加し、熱応力
に強いエピタキシヤルウエーハを得んとする試み
がなされているが、この場合には結晶の熱応力を
改善するのに十分な量の酸素を添加するにいたる
前に、酸素がエピタキシヤル成長を阻害するの
で、熱応力改善の目的を達することができないと
いう欠点があつた。Problems to be Solved by the Invention Attempts have been made to apply the above-mentioned known techniques to add oxygen during the epitaxial growth of silicon single crystals in order to obtain epitaxial wafers that are resistant to thermal stress. had the disadvantage that the purpose of improving thermal stress could not be achieved because oxygen inhibited epitaxial growth before a sufficient amount of oxygen was added to improve the thermal stress of the crystal.

問題点を解決するための手段 本発明は上述のごとき欠点を解決するため種々
研究の結果、意外にも窒素がこの熱応力改善に寄
与すること、およびこの窒素は酸素のようにエピ
タキシヤル成長を阻害することが全くないという
事実を知見し本発明に到達した。すなわち本発明
は、半導体シリコンのガス状化合物を熱分解もし
くは還元させ、ウエーハ上にシリコン単結晶をエ
ピタキシヤル成長させる方法において、該半導体
シリコンのガス状化合物を同伴するキヤリアガス
中またはエピタキシヤル成長雰囲気中に窒素ガス
またはアンモニアガスを0.1〜4vol％存在させる
ことを特徴とする窒素ドープシリコン単結晶の製
造方法である。Means for Solving the Problems In order to solve the above-mentioned drawbacks, the present invention has conducted various studies and found that, unexpectedly, nitrogen contributes to the improvement of thermal stress, and that nitrogen, like oxygen, does not support epitaxial growth. The present invention was achieved by discovering the fact that there is no inhibition at all. That is, the present invention provides a method for epitaxially growing silicon single crystals on a wafer by thermally decomposing or reducing a gaseous compound of semiconductor silicon, in a carrier gas or in an epitaxial growth atmosphere accompanied by the gaseous compound of semiconductor silicon. This is a method for producing a nitrogen-doped silicon single crystal, characterized in that nitrogen gas or ammonia gas is present in the amount of 0.1 to 4 vol%.

本発明者は、上述のように窒素の添加によりシ
リコン単結晶の熱応力改善をなし得たものである
が、これは窒素がシリコン結晶中において酸素と
同じような転位の固着作用をするためと考えられ
る。 The present inventor was able to improve the thermal stress of a silicon single crystal by adding nitrogen as described above, but this is because nitrogen acts to fix dislocations in the silicon crystal in the same way as oxygen. Conceivable.

つぎに本発明を図面によつて詳細に説明する。 Next, the present invention will be explained in detail with reference to the drawings.

第１図は本発明を実施する概略フロー図である
が、エピタキシヤル成長炉１を囲んでヒータ２を
配置し、該成長炉内に設けたサセプタ３の上にウ
エーハ４を必要数載置する。ヒータに電流を流し
て成長炉内を所定温度に加熱しながら、エピタキ
シヤル成長させる原料シリコン化合物ガスおよび
ドーパントガスをそれぞれ供給管５，６から流量
調節器（MFC）９，１０を経て成長炉内に送入
する。同時にキヤリアガスたとえば水素ガスを供
給管７より流量調節器１１を経て成長炉内に送入
し、また同伴ガスとして窒素ガスをキヤリアガス
に対し0.1〜4.0vol％の割合になるように流量調節
器１２を調節しながら供給管８より成長炉内に送
入する。成長炉内のエピタキシヤル雰囲気中に窒
素ガスを存在させるときも同じ比率とする。反応
を終えたガスはスクラバー１３より系外に排出さ
れる。通常この成長時間は、成長層の厚みにもよ
るが、５〜20分程度である。 FIG. 1 is a schematic flow diagram for implementing the present invention, in which a heater 2 is arranged surrounding an epitaxial growth furnace 1, and a necessary number of wafers 4 are placed on a susceptor 3 provided in the growth furnace. . While heating the inside of the growth furnace to a predetermined temperature by passing a current through the heater, the raw material silicon compound gas and dopant gas for epitaxial growth are fed into the growth furnace from supply pipes 5 and 6 through flow rate regulators (MFC) 9 and 10, respectively. Send to. At the same time, a carrier gas such as hydrogen gas is fed into the growth reactor from the supply pipe 7 via the flow rate regulator 11, and the flow rate regulator 12 is fed so that nitrogen gas as an accompanying gas has a ratio of 0.1 to 4.0 vol% to the carrier gas. It is fed into the growth furnace through the supply pipe 8 while being adjusted. The same ratio is used when nitrogen gas is present in the epitaxial atmosphere in the growth furnace. The gas that has completed the reaction is discharged from the system through the scrubber 13. Usually, this growth time is about 5 to 20 minutes, depending on the thickness of the growth layer.

これによつて、結晶中における窒素の含有量を
５×1013〜4.5×1015原子／cm3とすることができ
る。なお、結晶中の窒素含有量は、５×1013原
子／cm3未満では、本発明の目的とする熱応力改善
を達することができず、また4.5×1015原子／cm3
以上であると成長層の表面が荒れてくるという弊
害を生ずるようになる。 Thereby, the nitrogen content in the crystal can be set to 5×10 13 to 4.5×10 15 atoms/cm 3 . Note that if the nitrogen content in the crystal is less than 5×10 13 atoms/cm 3 , the thermal stress improvement that is the objective of the present invention cannot be achieved, and if the nitrogen content is less than 4.5×10 15 atoms/cm 3
If it is more than that, the surface of the growth layer will become rough.

またここにおける、窒素ガスの代わりにアンモ
ニアが用いられ、これを窒素分として前述の量が
含有されるように添加する。 In this case, ammonia is used instead of nitrogen gas, and is added so that the nitrogen content is contained in the above-mentioned amount.

本発明においてエピタキシヤル成長に用いられ
るウエーハは、シリコン単結晶、石英、サフアイ
ヤもしくは電気絶縁性セラミツクスたとえば窒化
シリコンの中から選ばれる。シリコンの成長層
は、一般には、シリコン単結晶ウエーハの場合に
10〜20μｍ、シリコン以外のウエーハでは１〜2μ
ｍ程度である。 The wafer used for epitaxial growth in the present invention is selected from single crystal silicon, quartz, sapphire or electrically insulating ceramics such as silicon nitride. The silicon growth layer is generally grown on silicon single crystal wafers.
10-20μm, 1-2μm for non-silicon wafers
It is about m.

本発明は前述のごとくシリコン単結晶ウエーハ
上に直接シリコン単結晶をエピタキシヤル成長さ
せる場合のほか、シリコン単結晶ウエーハ上に酸
化膜（SiO2）を開口部を残して形成させたのち、
この上にポリシリコンの成長層を形成させ、さら
にこの成長層をアニール法により再結晶化して単
結晶とする方法を含む。 In addition to epitaxially growing a silicon single crystal directly on a silicon single crystal wafer as described above, the present invention is also applicable to forming an oxide film (SiO 2 ) on a silicon single crystal wafer with openings left behind.
The method includes a method in which a polysilicon growth layer is formed on this, and then this growth layer is recrystallized by an annealing method to form a single crystal.

つぎに本発明の実施例を挙げる。 Next, examples of the present invention will be described.

実施例 CZ法により得られたＰ型＜100＞結晶方位を有
する直径100mm、抵抗率30Ωcmのシリコン単結晶
ウエーハ（サンプルＡ）をサセプター３上に載置
し、ついでこのウエーハを約1100℃に加熱しなが
ら、キヤリアガスH2にトリクロロシラン5.0vol
％、窒素ガス4.0vol％を配合して成長炉内に送入
し、20分間成長を行なわせたところ、厚さ20μ
ｍ、抵抗率40Ωcmの成長層を得た。このウエーハ
の窒素含有量は4.0×1015原子／cm3であつた。ま
た、同じ条件で窒素ガスを2.0vol％添加して成長
させたサンプルＢの窒素含有量は1.8×1015原
子／cm3であつた。なお、窒素ガス無添加で成長さ
せたサンプルＣの窒素含有量は測定検出限界以下
であつた。以上のサンプルＡ、Ｂ、Ｃについての
フオトルミネツセンス法による測定結果は、第２
図に示すとおりであり、サンプルＡ、Ｂについて
は明らかにＮのピークが認められた。Example A silicon single crystal wafer (sample A) with a diameter of 100 mm and a resistivity of 30 Ωcm and having a P type <100> crystal orientation obtained by the CZ method was placed on a susceptor 3, and then this wafer was heated to approximately 1100°C. While adding trichlorosilane 5.0vol to carrier gas H2
%, nitrogen gas 4.0 vol% was mixed into the growth furnace and grown for 20 minutes, resulting in a thickness of 20μ.
A grown layer with a resistivity of 40 Ωcm and a resistivity of 40 Ωcm was obtained. The nitrogen content of this wafer was 4.0×10 15 atoms/cm 3 . Further, the nitrogen content of sample B, which was grown under the same conditions with the addition of 2.0 vol % nitrogen gas, was 1.8×10 15 atoms/cm 3 . Note that the nitrogen content of Sample C grown without the addition of nitrogen gas was below the measurement detection limit. The measurement results of the above samples A, B, and C by the photoluminescence method are as follows.
As shown in the figure, an N peak was clearly observed for samples A and B.

発明の効果 本発明の方法によれば、エピタキシヤル成長を
阻害することなく熱応力に強いシリコン単結晶が
得られるので、半導体素子製造工程における熱処
理によつてもソリが発生することがなく、従来よ
り熱的に優れた素子を工業的に有利に製造するこ
とができる。Effects of the Invention According to the method of the present invention, silicon single crystals that are resistant to thermal stress can be obtained without inhibiting epitaxial growth. A device with better thermal properties can be advantageously manufactured industrially.

【図面の簡単な説明】[Brief explanation of drawings]

第１図は本発明を実施するための概略フロー図
を、第２図は実施例のシリコンエピタキシヤル層
中の窒素濃度測定のためのフオトルミネツセンス
法による測定結果を示す。 １……成長炉、２……ヒータ、３……サセプ
タ、４……ウエーハ、５，６，７，８……供給
管、９，１０，１１，１２……流量調節器
（MFC）、１３……スクラバー。 FIG. 1 is a schematic flowchart for carrying out the present invention, and FIG. 2 shows measurement results using a photoluminescence method for measuring nitrogen concentration in a silicon epitaxial layer in an example. 1... Growth furnace, 2... Heater, 3... Susceptor, 4... Wafer, 5, 6, 7, 8... Supply pipe, 9, 10, 11, 12... Flow rate controller (MFC), 13 ...Scrubber.

Claims (1)

【特許請求の範囲】 １ 半導体シリコンのガス状化合物を熱分解もし
くは還元させ、ウエーハ上にシリコン単結晶をエ
ピタキシヤル成長させる方法において、該半導体
シリコンのガス状化合物を同伴するキヤリアガス
中またはエピタキシヤル成長雰囲気中に窒素ガス
またはアンモニアガスを0.1〜4.0vol％存在させる
ことを特徴とする窒素ドープシリコン単結晶の製
造方法。 ２ 該ウエーハがシリコン単結晶、石英、サフア
イヤもしくは電機絶縁性セラミツクスから選ばれ
ることを特徴とする特許請求の範囲第１項記載の
方法。 ３ 該ウエーハとしてシリコン単結晶を用い、該
ウエーハ上に部分的に開口部を設けてなる酸化膜
を被覆処理した後シリコン結晶の成長を行なわ
せ、ついで該成長層の単結晶化を行わせることを
特徴とする特許請求の範囲第１項記載の方法。 ４ 半導体シリコンのガス状化合物がシリコンの
ハロゲン化合物から選ばれることを特徴とする特
許請求の範囲第１項、第３項記載のいずれかの方
法。 ５ 成長シリコン単結晶中に窒素が５×1013〜
4.5×1015原子／cm3含有されることを特徴とする
特許請求の範囲第１項、第３項記載のいずれかの
方法。[Scope of Claims] 1. A method for epitaxially growing silicon single crystals on a wafer by thermally decomposing or reducing a gaseous compound of semiconductor silicon, in which the gaseous compound of semiconductor silicon is entrained in a carrier gas or epitaxially grown. A method for producing a nitrogen-doped silicon single crystal, characterized in that nitrogen gas or ammonia gas is present in an atmosphere at 0.1 to 4.0 vol%. 2. The method according to claim 1, wherein the wafer is selected from silicon single crystal, quartz, sapphire or electrically insulating ceramics. 3. Using a silicon single crystal as the wafer, growing a silicon crystal after covering the wafer with an oxide film having an opening partially formed thereon, and then converting the grown layer into a single crystal. A method according to claim 1, characterized in that: 4. The method according to any one of claims 1 and 3, characterized in that the gaseous compound of semiconductor silicon is selected from halogen compounds of silicon. 5 Nitrogen in the grown silicon single crystal is 5×10 13 ~
The method according to any one of claims 1 and 3, characterized in that the content is 4.5×10 15 atoms/cm 3 .
JP9946384A 1984-05-17 1984-05-17 Preparation of nitrogen-doped silicon single crystal Granted JPS60246297A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP9946384A JPS60246297A (en) 1984-05-17 1984-05-17 Preparation of nitrogen-doped silicon single crystal

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP9946384A JPS60246297A (en) 1984-05-17 1984-05-17 Preparation of nitrogen-doped silicon single crystal

Publications (2)

Publication Number Publication Date
JPS60246297A JPS60246297A (en) 1985-12-05
JPH0371398B2 true JPH0371398B2 (en) 1991-11-13

Family

ID=14248003

Family Applications (1)

Application Number Title Priority Date Filing Date
JP9946384A Granted JPS60246297A (en) 1984-05-17 1984-05-17 Preparation of nitrogen-doped silicon single crystal

Country Status (1)

Country Link
JP (1) JPS60246297A (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4779519B2 (en) * 2005-09-08 2011-09-28 株式会社Ｓｕｍｃｏ Epitaxial wafer manufacturing method
TWI541864B (en) * 2012-12-06 2016-07-11 世創電子材料公司 Epitaxial wafer and its manufacturing method

Also Published As

Publication number Publication date
JPS60246297A (en) 1985-12-05

Similar Documents

Publication Publication Date Title
JP3524679B2 (en) High purity CVD-SiC semiconductor heat treatment member and method of manufacturing the same
JPH02302027A (en) Selective growth method for amorphous or polycrystalline silicon
JP4839646B2 (en) Silicon carbide semiconductor manufacturing method and silicon carbide semiconductor manufacturing apparatus
US4137108A (en) Process for producing a semiconductor device by vapor growth of single crystal Al2 O3
JP2742247B2 (en) Manufacturing method and quality control method for silicon single crystal substrate
Dumin et al. Heteroepitaxial growth of germanium and silicon on insulating substrates
Gupta et al. Silicon epitaxial layers with abrupt interface impurity profiles
JPH0371398B2 (en)
US3290181A (en) Method of producing pure semiconductor material by chemical transport reaction using h2s/h2 system
US3397094A (en) Method of changing the conductivity of vapor deposited gallium arsenide by the introduction of water into the vapor deposition atmosphere
US6183553B1 (en) Process and apparatus for preparation of silicon crystals with reduced metal content
JP2003209059A (en) Epitaxial silicon single crystal wafer and method of manufacturing the same
JPS6226569B2 (en)
Ishida et al. Growth and properties of Si films on sapphire with predeposited amorphous Si layers
JP2739469B2 (en) Method for growing SiC film
JP3494467B2 (en) Method of forming semiconductor thin film
EP0265988A1 (en) Epitaxial layers with controlled quantities of nitrogen, grown on silicon substrates and method for producing the same
JP2592984B2 (en) Manufacturing method of silicon thin film
Korec et al. Modeling of Sulfur Incorporation during Low Pressure CVD of GaAs (100) in the Ga‐HCl‐AsH3‐H 2‐H 2 S System
JPS6012775B2 (en) Method for forming a single crystal semiconductor layer on a foreign substrate
Manasevit Heteroepitaxial Silicon Growth Using SiH4 in Helium‐Hydrogen Atmospheres
Rao et al. SOS films and interfaces: Chemical aspects
JPH01179788A (en) Method for growing iii-v compound semiconductor on si substrate
JPS61264720A (en) Manufacture of polycrystalline silicon
Razouk et al. Publication costs of this article were assisted by Fairchild Camera and Instrument Corporation.

Legal Events

Date Code Title Description
EXPY Cancellation because of completion of term