JPS6362314A - Manufacture of semiconductor thin film - Google Patents
Manufacture of semiconductor thin filmInfo
- Publication number
- JPS6362314A JPS6362314A JP20819186A JP20819186A JPS6362314A JP S6362314 A JPS6362314 A JP S6362314A JP 20819186 A JP20819186 A JP 20819186A JP 20819186 A JP20819186 A JP 20819186A JP S6362314 A JPS6362314 A JP S6362314A
- Authority
- JP
- Japan
- Prior art keywords
- doping
- substrate
- thin film
- molecular beam
- semiconductor thin
- 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
- 239000004065 semiconductor Substances 0.000 title claims abstract description 12
- 239000010409 thin film Substances 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000000758 substrate Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 230000001678 irradiating effect Effects 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 17
- 229910052710 silicon Inorganic materials 0.000 abstract description 17
- 239000010703 silicon Substances 0.000 abstract description 17
- 229910052796 boron Inorganic materials 0.000 abstract description 12
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 11
- 239000010408 film Substances 0.000 description 11
- 239000012535 impurity Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 229910052814 silicon oxide Inorganic materials 0.000 description 5
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 229910052733 gallium Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 235000012431 wafers Nutrition 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- PEYVWSJAZONVQK-UHFFFAOYSA-N hydroperoxy(oxo)borane Chemical compound OOB=O PEYVWSJAZONVQK-UHFFFAOYSA-N 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Physical Deposition Of Substances That Are Components Of Semiconductor Devices (AREA)
Abstract
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は単結晶上の半導体薄膜の成長方法に関する。[Detailed description of the invention] [Industrial application field] The present invention relates to a method for growing semiconductor thin films on single crystals.
近年高速バイポーラ素子、マイクロ波用素子あるいは超
格子構造素子などへの応用を目的として、これまでのシ
リコン薄膜成長技術に比べ、より低温で成長が行われ、
従って不純物分布を乱すことがほとんどないという特徴
を有する、高真空内でのシリコン分子線成長(SiMB
E)技術が盛んに研究開発されている。In recent years, growth has been performed at lower temperatures than conventional silicon thin film growth techniques, with the aim of applying it to high-speed bipolar devices, microwave devices, superlattice structure devices, etc.
Therefore, silicon molecular beam growth (SiMB) in a high vacuum has the characteristic of hardly disturbing the impurity distribution.
E) Technology is being actively researched and developed.
このようなシリコン分子線成長技術においては、ドーピ
ング方法としてシリコンと同時に分子線セルから中世の
分子状もしくは原子状の不純物をとばす方法が一般的に
行われている。ドーピングのための不純物としては、分
子線セルから容易にとばすことができるアンチモン(n
型)、ガリウム(p型)に限られてきた。In such a silicon molecular beam growth technique, a method generally used for doping is to blow out medieval molecular or atomic impurities from a molecular beam cell at the same time as silicon. The impurity for doping is antimony (n), which can be easily removed from the molecular beam cell.
(type) and gallium (p-type).
しかし、現在の半導体素子製造プロセスにおいては、n
型不純物としてヒ素、リン、p型不純物としてホウ素が
使われており、これらの不純物に対する技術の蓄積も多
い、また、アンチモンでは固溶限は4X10”3−3で
あり、現在半導体プロセスにおいてヒ素によってつくら
れている10”aIl−のオーミック接触用高濃度不純
物領域を形成することができない、また、ガリウムはシ
リコン酸化膜中での拡散係数が非常に大きく、シリコン
酸化膜に接したガリウムドープ層中から酸化膜内へ拡散
してしまうので、通常のシリコン半導体製造プロセスで
は、まったく使われていない、また、素子構造をガリウ
ムドープ層が酸化膜と接しないような構造にしたとして
も、ガリウムの固溶限は1011al″″3程度なので
、ホウ素のような10”Ql”3のp型高濃度領域を作
ることができない。However, in the current semiconductor device manufacturing process, n
Arsenic and phosphorus are used as type impurities, and boron is used as p-type impurities, and there is a lot of accumulated technology for these impurities.Furthermore, the solid solubility limit of antimony is 4X10"3-3, and arsenic is currently used in semiconductor processes. It is not possible to form a high-concentration impurity region for ohmic contact of 10"aIl-, which is currently being created. Also, gallium has a very large diffusion coefficient in the silicon oxide film, and the gallium doped layer in contact with the silicon oxide film cannot be formed. Because it diffuses into the oxide film, it is not used at all in the normal silicon semiconductor manufacturing process.Also, even if the device structure is such that the gallium-doped layer does not come into contact with the oxide film, the solidity of gallium Since the solubility limit is about 1011al''3, it is not possible to create a p-type high concentration region of 10''Ql''3 like boron.
そこで、アール、ニー、ニー、クビアク(R,A、A。So, R, Knee, Kubiak (R, A, A).
Kubiak )等は、アプライド、フィジックス、レ
ターズ(Appl、Phys、Lett、) 44 (
9)(1984)878に述べられているように特殊な
ドーピング用セル内で単体のホウ素を〜2000℃に加
熱することによって、ホウ素によるドーピングを行い、
ホウ素のドーピング量が700℃から900℃の間でシ
リコン基板温度に依存しないことを見出した。しかし、
セル温度がまだ低いために、最高濃度は4X10” Q
1″″3に留っている。るつぼ材の耐熱性には限度があ
るためにセル温度をこれ以上あげることは難しい、さら
に、この方法ではセル温度が非常に高いためにホウ素以
外の物質が混入する危険が高く、また接近するセルとの
熱絶縁をとるのも難しい。Kubiak) etc. are Applied, Physics, Letters (Appl, Phys, Lett,) 44 (
9) (1984) 878 by heating elemental boron to ~2000°C in a special doping cell;
It has been found that the amount of boron doped is between 700°C and 900°C and does not depend on the silicon substrate temperature. but,
Since the cell temperature is still low, the maximum concentration is 4X10”Q
It remains at 1″″3. Because the heat resistance of the crucible material is limited, it is difficult to raise the cell temperature any higher.Furthermore, with this method, the cell temperature is very high, so there is a high risk of contamination with substances other than boron, and It is also difficult to provide thermal insulation from the
さらに、柏崎、辰巳等は、第17同面体素子材料コンフ
ァレンスのアブストラクトの301ページ(Ext−s
ndad Abstracts of the 17
th Confsrence on 5−olid 5
tate Devices and Materiar
ls、Tokyo、1985゜PP、301−304)
に述べられているように、拡散原料であるB20□及び
BNの混合物を通常のに一セル内で加熱することによっ
て、ホウ素によるドーピングを行い、最高濃度7X10
”aIl−’の高濃度ドーピングを達成している。しか
し、ドーピングソースとして酸化物を使用しているため
、高濃度ドーピングを行うとエピタキシャル膜内への酸
素の混入及び結晶性の悪化が問題となっている。また、
7X10” am−1はに一セルの耐熱限度1350
℃でしかも成長速度を下げて達成されたものであり、こ
れ以上の高濃度ドーピングは期待できない。Furthermore, Kashiwazaki, Tatsumi et al.
ndad Abstracts of the 17
th Confsrence on 5-olid 5
tateDevices and Materials
ls, Tokyo, 1985゜PP, 301-304)
As described in , doping with boron is carried out by heating a mixture of B20□ and BN as diffusion materials in a conventional cell to achieve a maximum concentration of 7X10.
High-concentration doping of "aIl-" has been achieved. However, since an oxide is used as a doping source, high-concentration doping causes problems such as oxygen incorporation into the epitaxial film and deterioration of crystallinity. Also,
7X10" am-1 cell heat resistance limit 1350
This was achieved at low temperature and at a low growth rate, and higher doping concentrations cannot be expected.
本発明の目的は、このような従来の欠点を除去し、シリ
コン分子線において、特殊なセルでなく通常使われてい
るクヌーセンセルを用いてホウ素を制御性良く、高濃度
にドーピングできる半導体薄膜の製造方法を提供するこ
とにある。The purpose of the present invention is to eliminate such conventional drawbacks and to develop a semiconductor thin film that can be doped with boron at a high concentration with good control using a commonly used Knudsen cell rather than a special cell in silicon molecular beams. The purpose is to provide a manufacturing method.
本発明は1分子線エピタキシャル法によって半導体薄膜
を基板上に形成する際に、HBO,を加熱することによ
って得た分子線を基板に照射することを特徴とする半導
体薄膜の製造方法である。The present invention is a method for producing a semiconductor thin film, which is characterized in that when a semiconductor thin film is formed on a substrate by a single molecular beam epitaxial method, the substrate is irradiated with a molecular beam obtained by heating HBO.
次に本発明の実施例について図面を参照して説明する。 Next, embodiments of the present invention will be described with reference to the drawings.
)IBO,はホウ素の拡散源として極めて高純度のもの
が得られる。市販のものは粉末であり、原料にはこれを
用いた。試料シリコン基板は、28%アンモニア水と3
0%過酸化水素水と水とを1:4:20の比率で混合し
、沸騰させた溶液中で10分間洗浄し、シリコン基板表
面に薄い酸化シリコン膜を形成し、次いで高真空中にて
短時間600℃ないし800℃に加熱し、その後高真空
中730℃以下にて電子ビーム蒸着法により、基板表面
の薄い酸化シリコン膜の上に薄い酸化シリコン膜の膜厚
の40%ないし80%の膜厚のシリコン薄膜を形成し、
しかる後に高真空中にて730℃以上で短時間加熱する
ことによって表面清浄を行った。ドーピング濃度は四探
針による抵抗値測定及びホール測定により求めた。結晶
欠陥密度は、通常用いられているライトエツチングを行
い、光学顕微鏡を用いてエッチピットを数えることによ
って求めた。)IBO, can be obtained as a boron diffusion source with extremely high purity. The commercially available powder was used as the raw material. The sample silicon substrate was mixed with 28% ammonia water and 3
Mix 0% hydrogen peroxide and water in a ratio of 1:4:20, wash in a boiling solution for 10 minutes to form a thin silicon oxide film on the silicon substrate surface, and then wash in a high vacuum. By heating to 600°C to 800°C for a short time, and then using electron beam evaporation in a high vacuum at 730°C or lower, a layer of 40% to 80% of the thickness of the thin silicon oxide film is deposited on the thin silicon oxide film on the substrate surface. Form a thick silicon film,
Thereafter, the surface was cleaned by heating at 730° C. or higher for a short time in a high vacuum. The doping concentration was determined by resistance value measurement using a four-probe probe and Hall measurement. The crystal defect density was determined by performing commonly used light etching and counting etch pits using an optical microscope.
第1図は1(BO2のセル温度と抵抗測定より求めたキ
ャリア濃度との関係をアレニウスプロットしたものであ
る。基板は、面方位が(100)で比抵抗が10〜20
Ω1であるn型シリコン基板である。成長温度は、70
0℃、成長速度は、IOA/s、成長膜厚は、1.5μ
であった。第1図より分かるようにプロットは直線上に
のり、最高濃度は6X10”GW″″′を達成すること
ができた。このような高濃度ドーピングは、柏崎、辰巳
等によって第17同面体素子材料コンファレンスのアブ
ストラクトの301ページ(Ext−ended Ab
stracts of the 17th Confe
ranes on 5−olid 5tate Dev
ices and Materials、Tokyo、
1985゜PP、301−304)に述べられている拡
散原料であるB20、を用いては実現できない、比較の
ために第2図に820.からのドーピングの場合のセル
温度とキャリア濃度の関係を示す、活性化エネルギーは
B20゜からのドーピングでは5.4aVであり、B□
O1の活性化エネルギーに極めて近いが、HBO,から
のドーピングでは1 、5eVでありHBO,に近い。Figure 1 is an Arrhenius plot of the relationship between the cell temperature of 1 (BO2) and the carrier concentration determined from resistance measurements.
It is an n-type silicon substrate with a resistance of Ω1. The growth temperature is 70
0°C, growth rate IOA/s, grown film thickness 1.5μ
Met. As can be seen from Figure 1, the plot was on a straight line, and the highest concentration of 6X10"GW""' could be achieved. Such high concentration doping was proposed by Kashiwazaki, Tatsumi et al. Page 301 of conference abstracts (Ext-ended Ab
structs of the 17th Confe
ranes on 5-olid 5tate Dev
ices and materials, Tokyo,
For comparison, 820.820. is shown in Figure 2 for comparison, but cannot be realized using B20, which is a diffusion raw material described in 1985゜PP, 301-304). The activation energy, which shows the relationship between cell temperature and carrier concentration in the case of doping from B20°, is 5.4aV when doping from B20°, and
The activation energy is very close to that of O1, but in the case of doping from HBO, it is 1.5 eV, which is close to HBO.
第3図にB、 O。B and O in Figure 3.
とI(BO,の蒸気圧の比較を示す、この図かられかる
ように900℃でI(BO,の蒸気圧はB20.の10
”倍も高く同じ10−’at+aの蒸気圧を得るのに必
要な温度はHBO3では870℃なのに対しB20.で
は1300℃が必要となる。これはドーピング時に同じ
不純物濃度を得るために必要な2つのB源のセル温度の
違いに対応する1以上の結果より820.からのドーピ
ングでは蒸発する分子は8□01であるが、 HBO,
からのドーピングではHBO,であると考えることがで
きる。従って、HBO□からのドーピングの場合には、
蒸気圧が高くなり、B20.の場合に比べて低いセル温
度でより高濃度のドーピングが可能になると考えられる
。This figure shows a comparison of the vapor pressures of I(BO,
The temperature required to obtain the same vapor pressure of 10-'at+a, which is twice as high, is 870°C for HBO3, while 1300°C for B20. From the results of more than 1 corresponding to the difference in cell temperature of the two B sources, the number of molecules evaporated when doping from 820. is 8□01, but HBO,
It can be considered that the doping from HBO is HBO. Therefore, in the case of doping from HBO□,
The vapor pressure increases and B20. It is thought that a higher concentration of doping can be achieved at a lower cell temperature than in the case of .
成長中、ホウ素とともに飛来すると考えられるる酸素は
SIMS測定の結果、成長温度が700℃以上ではエピ
タキシャル膜内には取込まれないことがわかった。As a result of SIMS measurements, it was found that oxygen, which is thought to come flying together with boron during growth, is not incorporated into the epitaxial film when the growth temperature is 700° C. or higher.
以上述べたように、 HBO,をドーピングソースとし
て使用することによって、8203をドーピングソース
として用いる場合に比べて、より低いセル温度でより高
濃度のドーピングが可能になる効果があることは明らか
である。As described above, it is clear that using HBO as a doping source has the effect of enabling higher concentration doping at a lower cell temperature than when using 8203 as a doping source. .
なお、本実施例ではシリコンウェハーを対象としたが、
本発明の方法は表面にのみシリコンが存在する5O5(
Silicon on 5apphire)基板や更に
一般に5OI(Silicon on In5ulat
or)基板等にも当然適用できる。Note that although silicon wafers were targeted in this example,
The method of the present invention uses 5O5 (
Silicon on 5apphire) substrates and more generally 5OI (Silicon on In5ulat) substrates.
or) Of course, it can also be applied to substrates, etc.
さらに1本実施例ではエピタキシャル成長の場合につい
て述べたが多結晶へのドーピングの場合にも当然適用で
きる。Furthermore, in this embodiment, the case of epitaxial growth has been described, but it can of course also be applied to the case of doping polycrystals.
また1以上の説明では本発明をシリコン分子線成長技術
におけるドーピング方法に適用した場合を例にとって説
明したが、これに限られるものではなく集積回路製造等
のウェハー処理工程に広く一般的に適用できるものであ
る。In addition, in the above explanation, the present invention is applied to a doping method in silicon molecular beam growth technology, but the present invention is not limited to this, and can be generally applied to a wide range of wafer processing processes such as integrated circuit manufacturing. It is something.
以上、詳細に述べた通り本発明によれば、シリコン分子
線において、特殊なセルでなく通常使われているクヌー
センセルを用いてホウ素を制御性良く、高濃度にドーピ
ングできる効果を有するものである。As described in detail above, according to the present invention, boron can be doped at a high concentration with good controllability in a silicon molecular beam using a commonly used Knudsen cell instead of a special cell. .
第1図はHBO,のセル温度と抵抗測定より求めたキャ
リア濃度との関係をアレニウスプロットした図、第2図
はB、 03からのドーピングの場合のセル温度とキャ
リア濃度の関係を示す図、第3図はB30、とHBO,
の蒸気圧の比較を示す図である。Figure 1 is an Arrhenius plot of the relationship between the cell temperature of HBO and the carrier concentration determined from resistance measurement, and Figure 2 is a diagram showing the relationship between cell temperature and carrier concentration when doping from B,03. Figure 3 shows B30, and HBO,
It is a figure showing the comparison of the vapor pressure of.
Claims (1)
板上に形成する際に、HBO_2を加熱することによっ
て得た分子線を基板に照射することを特徴とする半導体
薄膜の製造方法。(1) A method for producing a semiconductor thin film, which comprises irradiating the substrate with molecular beams obtained by heating HBO_2 when forming the semiconductor thin film on the substrate by molecular beam epitaxial method.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP20819186A JPS6362314A (en) | 1986-09-03 | 1986-09-03 | Manufacture of semiconductor thin film |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP20819186A JPS6362314A (en) | 1986-09-03 | 1986-09-03 | Manufacture of semiconductor thin film |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS6362314A true JPS6362314A (en) | 1988-03-18 |
Family
ID=16552169
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP20819186A Pending JPS6362314A (en) | 1986-09-03 | 1986-09-03 | Manufacture of semiconductor thin film |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6362314A (en) |
-
1986
- 1986-09-03 JP JP20819186A patent/JPS6362314A/en active Pending
Non-Patent Citations (1)
Title |
---|
EXTENDED ABSTRACTS OF THE 18TH CONTERENCE OR SOLID STATE DEVICES AND MATERIALS=1986 * |
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