JPS5868936A - Formation of insulating film on semiconductor crystal - Google Patents
Formation of insulating film on semiconductor crystalInfo
- Publication number
- JPS5868936A JPS5868936A JP56167389A JP16738981A JPS5868936A JP S5868936 A JPS5868936 A JP S5868936A JP 56167389 A JP56167389 A JP 56167389A JP 16738981 A JP16738981 A JP 16738981A JP S5868936 A JPS5868936 A JP S5868936A
- Authority
- JP
- Japan
- Prior art keywords
- gas
- semiconductor crystal
- insulating film
- crystal
- reaction tube
- 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
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Formation Of Insulating Films (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、絶縁ゲート形ＭＩＳ電界効果トランジスタの
ゲート絶縁膜を形成する場合に適用し得る、半導体結晶
上への絶縁膜の形成法に関し、特にＶ族・元素就中燐Ｃ
Ｐ）を有するＩ−Ｖ族化合物半導体結晶上に、絶縁膜を
形成する場合に適用して好適なものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for forming an insulating film on a semiconductor crystal, which can be applied to forming a gate insulating film of an insulated gate MIS field effect transistor. Phosphorus C
This method is suitable for forming an insulating film on a group IV compound semiconductor crystal having P).
半導体結晶上へのｊ８縁編の形成法として従来、熱酸化
法により半導体結晶上に半導体結晶の材料の酸化物でな
る４！ｌ鎌膜を形成する方法、両極−化法により半導体
結晶上に半導体結晶の材料の酸化−でなる絶縁膜を形成
する方法、化学気相ｊｌｌｌｉｌｌＣ所１ｌＣｖＤ法）
によってＳｉＯ２，、Ｍ、０５等でなる絶縁膜を形成す
る方法等が提案されている。Conventionally, as a method for forming a j8 edge stitch on a semiconductor crystal, a thermal oxidation method is used to form an oxide of the material of the semiconductor crystal on the semiconductor crystal 4! Method of forming a sickle film, Method of forming an insulating film made of oxidation of semiconductor crystal material on a semiconductor crystal by bipolarization method, Chemical vapor phase CvD method)
proposed a method of forming an insulating film made of SiO2, M, 05, etc.
然し乍ら、従来提案されている方法の場合、半導体結晶
上の絶縁膜が半導体結晶の表面を劣化せしめて形成され
たり、半導体結晶上の絶縁膜が化学的にも電気的にも安
定なものとして形成されなかったり、半導体結晶上の絶
縁膜が耐圧の高いものとして形成されなかったりする欠
点を有していた。特に半導体結晶をＩｎＰ 、 ＩｎＧ
ａＡｓＰ等の燐（Ｐ）を有するＩｎＡ ｓ 等のｌ−ｖ
族化合物半導体結晶とする場）、その半導体結晶上に絶
縁膜を形成する過程で、半導体結晶の表面よりそれを構
成する燐（Ｐ）が蒸発したりし工絶縁膜が半導体結晶と
のなす界面に高い濃度の表面単位を有せしめてなるもの
として形成され、仁の為、半導体〜結晶上に絶縁膜を形
成してなる構成を用いて、半導体結晶を半導体Ｓ１絶縁
膜を絶縁体■とせる絶縁ゲート形電界効果トランジスタ
を製った場合、その半導体Ｓ及び金＠Ｍ（絶縁体Ｉ上の
ゲート電極）間の容量対電圧特性に大なるヒステリシス
特性を呈し、依って上述せる絶縁ゲート形ＭＩＳｗｌ界
効果トランジスタを製る場合に適用しても、その絶縁ゲ
ート形ＭＩ８電界効果トランジスタを所期の実用性のあ
るものとして製ることか出来ない等の欠点を有していた
。However, in the case of conventionally proposed methods, the insulating film on the semiconductor crystal is formed by deteriorating the surface of the semiconductor crystal, or the insulating film on the semiconductor crystal is formed as being chemically and electrically stable. However, the insulating film on the semiconductor crystal may not be formed with a high withstand voltage. In particular, semiconductor crystals such as InP and InG
l-v such as InAs with phosphorus (P) such as aAsP
In the process of forming an insulating film on the semiconductor crystal, the phosphorus (P) that makes up the semiconductor crystal evaporates from the surface of the semiconductor crystal. The structure is formed by forming an insulating film on a semiconductor to a crystal, and the semiconductor crystal is formed as a semiconductor with a high concentration of surface units, and the insulating film is an insulator. When an insulated gate field effect transistor is manufactured, it exhibits a large hysteresis characteristic in the capacitance vs. voltage characteristic between the semiconductor S and gold@M (gate electrode on the insulator I), and therefore the above-mentioned insulated gate MISWl. Even if it is applied to the production of field effect transistors, it has drawbacks such as the inability to produce insulated gate MI8 field effect transistors with desired practicality.
依って本発明は上述せる欠点のない新規な半導体結晶上
への絶縁膜の形成法を提案せんとするもので、以下本発
明の実施例を述べる所より明らかとなるであろう。Therefore, the present invention proposes a novel method for forming an insulating film on a semiconductor crystal without the above-mentioned drawbacks, and this will become clear from the following description of embodiments of the present invention.
本発明の実施例に於ては、塩化硫黄（５ｏ１２）ガスの
得られるガス源１ 、 Ｈ，ＰＳ４ガスの得られるガス
源２、ホスフィン（ＰＨ，）ガスを含む水素（Ｈ）ガス
の得られるガス源５、及び塩化水素（ＨＯＪ ’）ガス
を含む水素（Ｈ）ガスの得られるガス源４を夫々弁５１
．６．７及び８を介して連結してなる反応管１０が用意
される。この場合ガス源１，２．５及び４は、反応管１
０の一気管９が導出されている。尚反応管１０の周りに
加熱源１１が配されているものとする。In the embodiment of the present invention, a gas source 1 from which sulfur chloride (5o12) gas is obtained, a gas source 2 from which H, PS4 gas is obtained, and a hydrogen (H) gas containing phosphine (PH,) gas is obtained. A gas source 5 and a gas source 4 from which hydrogen (H) gas containing hydrogen chloride (HOJ') gas is obtained are connected to valves 51, respectively.
．． A reaction tube 10 connected via 6.7 and 8 is prepared. In this case gas sources 1, 2.5 and 4 are reactor tube 1
0 trachea 9 is led out. It is assumed that a heat source 11 is arranged around the reaction tube 10.
而して先ず、反応管１０内にＩｎＰ結晶でなる半導体結
晶１２を適当な手段（図示せず）を用いて設置する。First, a semiconductor crystal 12 made of InP crystal is placed in the reaction tube 10 using an appropriate means (not shown).
次に弁６を予定の時間だけ開いて反応管１０内に予定の
時間だけガス源４よりの塩化水素（Ｈｏｄ ）ガスを含
む水素（Ｈ）ガスを流し、その塩化水素（ＨＯｌ）ガス
による半導体結晶１２の表面に対する軽いエツチング処
理をなさしめ、依って半導体結晶１２の表面を清浄化す
る。Next, the valve 6 is opened for a predetermined time to flow hydrogen (H) gas containing hydrogen chloride (Hod) gas from the gas source 4 into the reaction tube 10 for a predetermined time. A light etching process is performed on the surface of the crystal 12, thereby cleaning the surface of the semiconductor crystal 12.
次に弁７を開き、反応管１０内にガス源５よりのホスフ
ィン（ＰＨ，）ガスを含む水素（Ｈ）ガスを流し、反応
管１０内がホスフィン（ＰＨ，）ガスを含む水素（Ｈ）
ガスにて全く置換せしめられた所で、加熱源１１により
反応管１０を加熱せしめ、半導体結晶１２を２８０℃５
５２０℃の温度就中約５００℃の温度に加熱する。この
場合半導体結晶１２の表面よりそれを構成する燐（Ｐ）
が蒸発せんとしても、反応管１０内にホスフィン（ＰＨ
５）ガスを含む水素（Ｈ）ガスが流され、この為反応管
１０内にホスフィン（Ｐｉ（、）ガスの分解により生じ
た燐（Ｐ）の分圧を有するので、半導体結晶１２の−Ｓ
面よりそれを構成する燐ＣＰ）が不必要に蒸発すること
がないものである。Next, the valve 7 is opened and hydrogen (H) gas containing phosphine (PH,) gas from the gas source 5 is flowed into the reaction tube 10, so that the inside of the reaction tube 10 is filled with hydrogen (H) containing phosphine (PH,) gas.
After the gas has been completely replaced, the reaction tube 10 is heated by the heating source 11, and the semiconductor crystal 12 is heated to 280°C.
Heat to a temperature of 520°C, preferably about 500°C. In this case, phosphorus (P) constituting the semiconductor crystal 12 is
Even if phosphine (PH) does not evaporate, phosphine (PH
5) Hydrogen (H) gas containing gas is flowed, and as a result, there is a partial pressure of phosphorus (P) generated by the decomposition of phosphine (Pi (,) gas in the reaction tube 10, so -S of the semiconductor crystal 12
The phosphorus (CP) constituting the surface does not evaporate unnecessarily.
次に斯く加熱＠、１１により、半導体結晶１２を２８０
℃〜５２０℃就中約５００℃に加熱せしめている状態で
、弁７を閉じ、ガス＃５よりのホスフィン（ＰＨ，”）
ガスをｆむ水素Ｃ□）ガスの反応管１Ｄ内への供給を断
とし、これに代え弁５及び６を開き、反応管１０内に、
ガス源１からの塩化硫黄（８０）、）ガスを流すと共に
ガス源２からの）（、Ｐ８４ガスを流し、反応管１０内
で塩化硫黄（５ｏ１２） ガスとＨｓＰＳ４ガスとを
気相反応せしめる。然るときは、塩化値＊ （８０４’
２）ガスと１４．ＰＳ４カスとの反応により“、硫化燐
（Ｐ４Ｓ、）と塩化水素（塩酸）とが生成し、その硫化
燐（Ｐ４８． ） が半導体結晶１２上に堆積すると
いう機構で、半導体結晶１２上に硫化燐（ｐ４ｓ、 ）
でなる絶縁膜１１５が形成されるものである。Next, by heating 11 in this manner, the semiconductor crystal 12 is heated to 280°C.
℃~520℃, with the valve 7 closed and the phosphine (PH,'') from gas #5 heated to about 500℃.
Hydrogen C□) Cut off the gas supply into the reaction tube 1D, open the valves 5 and 6 instead, and add the hydrogen into the reaction tube 10.
The sulfur chloride (80) gas from the gas source 1 and the P84 gas from the gas source 2 are caused to react in the gas phase between the sulfur chloride (5o12) gas and the HsPS4 gas in the reaction tube 10. In that case, the chloride value* (804'
2) Gas and 14. Through the reaction with PS4 residue, phosphorus sulfide (P4S) and hydrogen chloride (hydrochloric acid) are generated, and the phosphorus sulfide (P48.) is deposited on the semiconductor crystal 12. Phosphorus (p4s, )
An insulating film 115 is formed.
以上にて本発明の方法の実施告が明らかとなったが、斯
る方法によれば、ＩｎＰ結晶でなる半導体結晶１２の配
されてなる反応管１０内で、塩化硫黄（５ｏ１２）
ガスとＨ３Ｐ５４ガスとを気相反応せしめる工程を含ん
で、半導体結晶１２上に硫化燐（Ｐ４８． ） でな
る絶縁膜１５を形成せしめるものであるが、この場合、
絶縁膜１３が燐（Ｐ）を含む雰囲気しかも半導体結晶１
２が２８０℃〜５２０℃就中約５００℃という比較的低
い温度で加熱されているという状態で形成され、又絶縁
膜１５′自身が燐（Ｐ）を含む硫化硫（Ｐ４８． ）
で得られるので、半導体結晶１２がＩｎＰ結晶でなる
ことにより、その表面よりそれを構成する燐（Ｐ）が蒸
興せんとしてもそれが効果的に抑圧され、従って絶縁ｌ
１１１５が半導体結晶１２とのなす界面に高い濃度の表
面準位を有せしめているものとして形成されることがな
いものである。この為本発明の方法によって半導体結晶
１２上に絶縁膜１５を形成してなる構成を用いて、半導
体結晶を半導体５１ｉｌ！３縁編１５を絶縁体■とせる
絶縁ゲート形嵐界効米トランジスタを製った場合、その
半導体Ｓ及び金属Ｍ（絶縁体■上のゲート成極）間の容
量対電圧特性に犬なるヒステリシス特性を呈さす、依っ
て本発明による方法を上述せる絶縁ゲート形ＭＩ ８ｍ
界効果トランジスタを製る場合に適用しても、その絶縁
ゲート形ＭＩＳ電界効果トランジスタを所期の実用性の
あるものとして製ることが出来るという大なる＄９を有
するものである。The implementation of the method of the present invention has been clarified above, and according to this method, sulfur chloride (5o12) is
The method includes a step of causing a gas phase reaction with H3P54 gas to form an insulating film 15 made of phosphorus sulfide (P48.) on the semiconductor crystal 12. In this case,
The insulating film 13 is in an atmosphere containing phosphorus (P) and the semiconductor crystal 1
The insulating film 15' itself is formed of sulfur sulfide (P48.) containing phosphorus (P).
Therefore, by making the semiconductor crystal 12 an InP crystal, even if the phosphorus (P) constituting it does not evaporate from its surface, it is effectively suppressed, and therefore the insulation l
Since 1115 has a high concentration of surface states at the interface with the semiconductor crystal 12, it is not formed. For this reason, a structure in which an insulating film 15 is formed on a semiconductor crystal 12 by the method of the present invention is used to form a semiconductor crystal 51il! When an insulated gate type storm field effect transistor is manufactured in which the third edge 15 is an insulator, there is a significant hysteresis in the capacitance versus voltage characteristics between the semiconductor S and the metal M (gate polarization on the insulator). The insulated gate type MI 8m exhibiting the characteristics and thus the method according to the invention described above
Even when applied to the production of field effect transistors, it is possible to produce insulated gate type MIS field effect transistors with the desired practicality, which is a significant cost of $9.
又本発明の方法によれば、絶縁膜１５が硫化燐（Ｐ４Ｓ
、 ’） で得られ、而してその硫化溝ＣＰ４Ｓ、
）が化学的にも電気的にも比較的安定であるので、半導
体結晶１２上の絶縁膜１５を化学的にも一気的にも比較
的安定なものとして形成し得るものである。Further, according to the method of the present invention, the insulating film 15 is made of phosphorus sulfide (P4S).
, '), and its sulfide groove CP4S,
) is relatively stable both chemically and electrically, so that the insulating film 15 on the semiconductor crystal 12 can be formed relatively stable both chemically and at once.
更に絶縁膜１５が硫化燐（Ｐ４Ｓ７）で祷られ、而して
その硫化燐（Ｐ４Ｓ７．）でなる絶縁膜１５は比較的高
い耐圧を有するので、半導体結晶１２上の絶縁膜１５を
耐圧の高いものとして形成し得るものである等の％徴も
併せ有するものである。Furthermore, the insulating film 15 is made of phosphorus sulfide (P4S7), and the insulating film 15 made of phosphorus sulfide (P4S7.) has a relatively high withstand voltage. It also has the characteristic of being able to be formed as a product.
尚上述に於ては、反応管１０内で塩化硫黄（ＦＫＪＩ２
） ガスとＨ，Ｐ８４ガスとを気相反応せしめるべく
、それ等ガスを略々同じ時点より反応管１０内に流すも
のとして述べたものであるが、先ずＨ，Ｐ８４易’スの
みを反応管１０内に流して半導体結晶１２の表面をＨ３
Ｐ８４ ガスによって予め硫化せしめ、次で反応管１
０内に塩化硫黄（ＳＣＭ、 ＞ ガスをＨ３Ｐ５４ガ
スと共に流し、これにより塩化硫黄（８Ｃ１２’）
ガスとＨ，ＰＳ４ガスとを気相反応せしめる様になすこ
とも出来、斯くしても半導体結晶１２上に硫化燐（Ｐ４
Ｓ７）でなる絶縁膜１５を形成することが出来、又この
場合も、上述せる優れた特徴を以って絶縁膜１５を形成
し得るものである。In the above description, sulfur chloride (FKJI2
) In order to cause a gas phase reaction between the gas and the H and P84 gases, it is assumed that these gases are flowed into the reaction tube 10 from approximately the same point in time. 10 to coat the surface of the semiconductor crystal 12 with H3.
P84 Preliminarily sulfurized with gas, then reactor tube 1
Sulfur chloride (SCM, > gas is flowed together with H3P54 gas in the
It is also possible to cause a gas phase reaction between the gas and H, PS4 gas, and in this way, phosphorus sulfide (P4
The insulating film 15 made of S7) can be formed, and also in this case, the insulating film 15 can be formed with the above-mentioned excellent characteristics.
又上述に於ては半導体結晶１２がＩｎＰ結晶である場合
につき述べたが、 Ｉｎ（ｈＡｓＰの如き燐（Ｐ）を有
するｉ−ｖ族化合物半導体結晶である場合にも本発明を
適用して、上通せる讃れた特徴を以って硫化溝（Ｐ４８
． ） でなる絶縁膜。Although the above description has been made regarding the case where the semiconductor crystal 12 is an InP crystal, the present invention can also be applied to a case where the semiconductor crystal 12 is an IV group compound semiconductor crystal containing phosphorus (P) such as In(hAsP). Sulfide groove (P48)
．． ) An insulating film made of
１５を形成し得ること明らかであろう。It will be clear that 15 can be formed.
その他事発明の精神を脱することなしにｉ々の変型変更
をなし得るであろう。Other modifications may be made without departing from the spirit of the invention.
図は本発明による半纏体結話上への絶縁膜の形成法の説
明に供する噌線図である。
図中、１．２．５及び４はガス諒、５．６．７及び８は
弁、９は排気、管、１０は反応管、１１は加熱ω、１２
）ま半導体結ａａ、１５は絶縁・腺を大々示す。
出願人 日本域信域話公社The figure is a diagram illustrating a method of forming an insulating film on a semi-woven fabric according to the present invention. In the figure, 1.2.5 and 4 are gas pipes, 5.6.7 and 8 are valves, 9 is exhaust pipe, 10 is reaction tube, 11 is heating ω, 12
) Ma semiconductor connection aa, 15 shows insulation/gland. Applicant: Japan Area Communication Corporation
Claims (1)
１，） ガスとＨ，Ｐｆ９４ガスとを気相反応せしめ
る工程を含んで、上記半導体結晶上に硫化燐（Ｐ４８ア
）でなる絶縁膜を形成せしめる事を特徴とする半導体結
晶上への絶縁膜の形成法。Sulfur chloride (80%
1.) An insulating film on a semiconductor crystal characterized by forming an insulating film made of phosphorus sulfide (P48A) on the semiconductor crystal, including a step of causing a gas phase reaction with H, Pf94 gas. Formation method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56167389A JPS5868936A (en) | 1981-10-20 | 1981-10-20 | Formation of insulating film on semiconductor crystal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56167389A JPS5868936A (en) | 1981-10-20 | 1981-10-20 | Formation of insulating film on semiconductor crystal |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS5868936A true JPS5868936A (en) | 1983-04-25 |
Family
ID=15848791
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56167389A Pending JPS5868936A (en) | 1981-10-20 | 1981-10-20 | Formation of insulating film on semiconductor crystal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5868936A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2604826A1 (en) * | 1986-10-06 | 1988-04-08 | France Etat | METHOD OF FORMING AN INSULATING LAYER COMPRISING SULFIDE, SULFIDE DERIVATIVES OBTAINED AND APPARATUS FOR IMPLEMENTING THE METHOD |
| US4871692A (en) * | 1988-09-30 | 1989-10-03 | Lee Hong H | Passivation of group III-V surfaces |
-
1981
- 1981-10-20 JP JP56167389A patent/JPS5868936A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2604826A1 (en) * | 1986-10-06 | 1988-04-08 | France Etat | METHOD OF FORMING AN INSULATING LAYER COMPRISING SULFIDE, SULFIDE DERIVATIVES OBTAINED AND APPARATUS FOR IMPLEMENTING THE METHOD |
| US4871692A (en) * | 1988-09-30 | 1989-10-03 | Lee Hong H | Passivation of group III-V surfaces |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI220269B (en) | Method for fabricating n-type carbon nanotube device | |
| JPH0198242A (en) | Formation of single crystal magnesia spinel film | |
| JP2001244464A (en) | Method of manufacturing metal oxide transistor | |
| JPH03187215A (en) | Manufacture of silicon thin film | |
| JPS5868936A (en) | Formation of insulating film on semiconductor crystal | |
| WO2018149017A1 (en) | Method for preparing tin-doped n-type gallium oxide | |
| JPH046835A (en) | Compound semiconductor device | |
| JPS6362095B2 (en) | ||
| JPS5868937A (en) | Formation of insulating film on semiconductor crystal | |
| JPS63119268A (en) | Manufacture of semiconductor device | |
| JPH01283872A (en) | Manufacture of mis type semiconductor device | |
| KR960004902B1 (en) | Preparation of polycrystalline silicon thin film | |
| KR950007671B1 (en) | Method for evaporation a thin film of tungsten | |
| JP2003243314A (en) | Method of manufacturing diamond film and method of manufacturing electronic device using it | |
| JPS6110233A (en) | Manufacture of semiconductor device | |
| JPS63115325A (en) | Silicon thin film and manufacture thereof | |
| JPH034532A (en) | Manufacture of compound semiconductor device | |
| JPS62116773A (en) | Electrically conductive transparent film | |
| JPH01227475A (en) | Amorphous silicon thin-film transistor | |
| JPS63103893A (en) | Production of 6h-sic substrate | |
| JPS61248566A (en) | Semiconductor non-volatile memory | |
| JPS6390833A (en) | Manufacture of compound thin film of group ii and vi elements | |
| JPH0442926A (en) | Compound semiconductor crystal having insulating layer on surface | |
| KR910001892A (en) | Phosphorus Doped Oxide Flow Process Method | |
| JPH033330A (en) | Formation of insulating film onto semiconductor crystal substrate |