JPH04110471A - Formation of thin film - Google Patents
Formation of thin filmInfo
- Publication number
- JPH04110471A JPH04110471A JP22967890A JP22967890A JPH04110471A JP H04110471 A JPH04110471 A JP H04110471A JP 22967890 A JP22967890 A JP 22967890A JP 22967890 A JP22967890 A JP 22967890A JP H04110471 A JPH04110471 A JP H04110471A
- Authority
- JP
- Japan
- Prior art keywords
- gas
- substrate
- halogen
- light
- plasma
- 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
- 239000010409 thin film Substances 0.000 title claims abstract description 13
- 230000015572 biosynthetic process Effects 0.000 title claims description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 42
- 150000002367 halogens Chemical class 0.000 claims abstract description 42
- 230000001678 irradiating effect Effects 0.000 claims abstract description 9
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 8
- 239000000758 substrate Substances 0.000 claims description 66
- 239000010408 film Substances 0.000 claims description 55
- 238000000034 method Methods 0.000 claims description 23
- 238000000151 deposition Methods 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 92
- 229910052760 oxygen Inorganic materials 0.000 abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 16
- 239000001301 oxygen Substances 0.000 abstract description 16
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract 3
- 239000004065 semiconductor Substances 0.000 description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910021417 amorphous silicon Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 3
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- -1 Ca2 Chemical class 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910007264 Si2H6 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Landscapes
- Chemical Vapour Deposition (AREA)
- Formation Of Insulating Films (AREA)
- Thin Film Transistor (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分!l’l’ ]
本発明は薄膜形成方法に関し、更に詳しくは半導体素子
の絶縁膜形成方法に関するものであり、特に電界効果型
]・ランジスタに好適に用いることのできる絶縁膜形成
方法に関する。[Detailed description of the invention] [Industrial use! The present invention relates to a method for forming a thin film, and more particularly to a method for forming an insulating film for semiconductor devices, and particularly to a method for forming an insulating film that can be suitably used for field effect type transistors.
[従来技術の説明]
従来、単結晶シリコンを用いたM OS型FETのゲー
ト絶縁膜は一般に単結晶シリコンを酸化雰囲気中で90
0〜]100°Cに加熱処理する事で形成されている。[Description of Prior Art] Conventionally, the gate insulating film of a MOSFET using single crystal silicon is generally made by heating single crystal silicon in an oxidizing atmosphere at 90°C.
It is formed by heat treatment at 0~]100°C.
又、アモルファスシリコン(以下、a−Siと称する)
、多結晶シリコンを半導体層とするTPTあるいはIn
P GaA、sなどのMIS型FETのグー1〜絶縁
膜は一般にスパッタ法、熱CVD法、プラズマCVD法
等により形成されている。Also, amorphous silicon (hereinafter referred to as a-Si)
, TPT or In with polycrystalline silicon as the semiconductor layer
Insulating films of MIS type FETs such as P GaA and S are generally formed by a sputtering method, a thermal CVD method, a plasma CVD method, or the like.
[発明が解決しようとしている課題]
しかし、SOI構造のM OS F E Tを三次元構
造の半導体装置に応用する場合のように、半導体装置を
三次元的に形成する場合には、半導体層が多層形成され
る。このために熱エネルギーを用いて上層のデバイスを
形成すると、下層のデバイスの半導体層が熱によるダメ
ージを受ける心配がある。[Problem to be solved by the invention] However, when forming a semiconductor device three-dimensionally, such as when applying an SOI structure MOSFET to a three-dimensional structure semiconductor device, the semiconductor layer is Formed in multiple layers. For this reason, if thermal energy is used to form the upper layer device, there is a risk that the semiconductor layer of the lower layer device will be damaged by the heat.
又、ガラス上の多結晶Sjあるいは単結晶Slを用いる
デバイスにおいても、ガラス基板が熱的ダメージを受け
るため、ゲー[・絶縁膜の作製法として熱酸化法を用い
る事が難しい。Furthermore, even in devices using polycrystalline Sj or single-crystalline Sl on glass, it is difficult to use thermal oxidation as a method for producing a gaming insulating film because the glass substrate is thermally damaged.
更に、ゲート絶縁膜としてスパッタ法あるいはプラズマ
CVD法を用いた場合には、加速されたイオンによって
半導体層にダメージが生じるため、半導体層と絶縁膜の
界面準位が多くなり、キャリアの移動度の低下等を招き
素子性能の劣化を生ずる場合があった。Furthermore, when sputtering or plasma CVD is used to form a gate insulating film, the semiconductor layer is damaged by accelerated ions, which increases the interface states between the semiconductor layer and the insulating film, which reduces carrier mobility. This may lead to deterioration of device performance.
[本発明の目的1
本発明の目的は、従来にLヒベて格段に素子性能を向」
ニさせることができる薄膜形成方法を提案することであ
る。[Objective of the present invention 1] An object of the present invention is to significantly improve device performance over conventional L.
The purpose of the present invention is to propose a method for forming a thin film that can achieve the following effects.
また、本発明の目的は、半導体層と絶縁膜の界面準位を
減少させることができる薄膜形成法を提案することにあ
る。Another object of the present invention is to propose a thin film forming method that can reduce the interface states between a semiconductor layer and an insulating film.
更に本発明は基体へ前処理を行い、半導体層と絶縁膜の
界面準位を減少させることのできる薄膜形成方法を提案
することを目的としている。A further object of the present invention is to propose a method for forming a thin film that can reduce the interface states between a semiconductor layer and an insulating film by subjecting a substrate to pretreatment.
[課題を解決するための手段]
本発明は、従来技術の持つ課題を解決すべく鋭意研究を
重ねた結果完成に至ったものであり、本発明の薄膜形成
方法は、プラズマと光を用いて成膜を行う成膜方法成に
おいて、基体の配された成膜室内にハロゲンガスを導入
する工程と、前記ハロゲンガスを励起し前記基体を処理
するハロゲン処理工程と、前記ハロゲン処理後、励起し
ても単独では堆積しない第1のガスを基体の配された反
応容器、内に導入する工程と、前記反応容器内に導入さ
れた前記第1のガスをプラズマ励起する工程と、第2の
ガスを前記反応容器内に導入し、前記励起された第1の
ガスと反応させ、生成した反応生成物を基体」二に(=
1着せしめ、前記反応生成物が付着する基体に光を照射
する工程とを有することを特徴どするものである。また
は、プラズマと光を用いて成膜を行う成膜方法において
、基体の配された成膜室内にハロゲンガスな導入する工
程と、前記ハロゲンガスを励起し前記基体を処理するハ
ロゲン処理工程と、前記ハロゲン処理後、励起しても単
独では堆積しない第1のガスを基体の配された反応容器
内に導入する工程と、前記反応容器内に導入された前記
第1のガスをプラズマ励起する工程と、前記ハロゲン処
理後の基体を励起された前記第1のガスにさらす工程と
、第2のガスを前記反応容器内に導入し、前記励起され
た第1のガスと反応させ、生成した反応生成物を基体上
に付着せしめ、前記反応生成物が付着する基体に光を照
射する工程とを有することを特徴とするものである。[Means for Solving the Problems] The present invention was completed as a result of intensive research to solve the problems of the prior art, and the thin film forming method of the present invention uses plasma and light. A film forming method for forming a film includes a step of introducing a halogen gas into a film forming chamber in which a substrate is arranged, a halogen treatment step of exciting the halogen gas and treating the substrate, and a step of exciting the halogen gas after the halogen treatment. a step of introducing into a reaction vessel in which a substrate is arranged a first gas which is not deposited alone even if is introduced into the reaction vessel and reacted with the excited first gas, and the generated reaction product is transferred to the substrate.
The method is characterized by comprising a step of applying light to the substrate to which the reaction product is attached. Alternatively, in a film forming method in which a film is formed using plasma and light, a step of introducing a halogen gas into a film forming chamber in which a substrate is arranged, and a halogen treatment step of exciting the halogen gas and treating the substrate; After the halogen treatment, a step of introducing a first gas that does not deposit on its own even when excited into a reaction container in which a substrate is arranged, and a step of plasma exciting the first gas introduced into the reaction container. a step of exposing the substrate after the halogen treatment to the excited first gas; and a step of introducing a second gas into the reaction vessel and reacting with the excited first gas, resulting in a reaction. The method is characterized by comprising the steps of depositing a product on a substrate and irradiating the substrate to which the reaction product is deposited with light.
[作用]
本発明によれば成膜を行う基体表面に前処理どしてハロ
ゲン処理、もしくはハロゲン処理に続りて第1のガスに
よる処理を行うことによって基体表面と半導体との界面
準位密度を大幅に減少することができる。また光とプラ
ズマを用いる成膜方法を用いることによって低温下で処
理が行え、しかも成膜時と同じ光源およびプラズマ源を
用いることによってより効果的に前処理を行うことがで
きる。特に低温で処理を行いえることは、ハロゲン処理
を行う場合、特に好ましいものである。[Function] According to the present invention, the interface state density between the substrate surface and the semiconductor is reduced by pre-treating the surface of the substrate on which a film is to be formed and performing halogen treatment, or by performing treatment with a first gas following the halogen treatment. can be significantly reduced. Further, by using a film formation method using light and plasma, processing can be performed at low temperatures, and moreover, by using the same light source and plasma source as used for film formation, pretreatment can be performed more effectively. In particular, the ability to perform the treatment at low temperatures is particularly preferred when performing halogen treatment.
本発明において、界面準位密度がハロゲンガスあるいは
ハロゲンガスに続いて行われる第1のガスによる前処理
で低減する理由は以下に示される機構によるものど考え
られる。In the present invention, the reason why the interface state density is reduced by the halogen gas or the first gas pretreatment performed subsequent to the halogen gas is thought to be due to the following mechanism.
一般に半導体素子の製造を行う際に使用されるSj基体
は、不純物除去の点からエツチング液としてフッ酸(H
F )溶液を用いたエツチングを行った後、超純水での
洗浄が行われている。そしてこれらの基体表面のSiの
ダングリングボンドは水素原子によりターミネートされ
ており、酸化されにくいことが知られている。よって例
えばこの表面にSiO2膜をCVD法により形成する場
合には、基体表面にS j−1−1結合が存在するため
、Sjど酸素とが直接結合しにくい。このため基体表面
において不完全な反応が生じ、界面に多くのS j−H
結合が残存したり、また5j−OH結合等が形成されて
い界面準位密度が高くなってしまうと考えられる。これ
に対してSiウェハを例えばF等のハロゲン原子の励起
種で処理する事によって、界面のS i −1−1結合
の1丁を効率よ(Fに置換することができ、水素を取り
除くことができる。5j−F結合のFとOとの置換はゴ
]と0との置換に比べて起こり易いため、5jO)2膜
を形成する場合の第1のガスである酸素の励起種(プラ
ズマ励起、及び/又は光励起によって得られる)に基体
をさらす処理を行うことで、FとOの置換を行い、さら
に良好で安定な5j−0結合を得ることができる。この
ように基体表面のSiどOとの結合を効率よく行わせる
ことによって、SjとSiO□膜間の界面準位密度を低
減することができる。Sj substrates, which are generally used when manufacturing semiconductor devices, are treated with hydrofluoric acid (H) as an etching solution to remove impurities.
F) After etching using a solution, cleaning with ultrapure water is performed. It is known that the Si dangling bonds on the surface of these substrates are terminated with hydrogen atoms and are difficult to oxidize. Therefore, for example, when a SiO2 film is formed on this surface by the CVD method, since Sj-1-1 bonds exist on the substrate surface, direct bonding between Sj and oxygen is difficult. Therefore, an incomplete reaction occurs on the substrate surface, and many S j-H
It is considered that the interface state density becomes high due to remaining bonds or formation of 5j-OH bonds. On the other hand, by treating the Si wafer with an excited species of halogen atoms such as F, one of the Si-1-1 bonds at the interface can be efficiently replaced with F, and hydrogen can be removed. Since the substitution of F and O in the 5j-F bond occurs more easily than the substitution of G] and 0, the excited species of oxygen (the plasma By exposing the substrate to (obtained by excitation and/or photoexcitation), F and O can be substituted, and an even better and more stable 5j-0 bond can be obtained. By efficiently bonding Si and O on the substrate surface in this way, the interface state density between Sj and the SiO□ film can be reduced.
[実施例]
本発明においては、半導体の基体上に絶縁膜を形成する
場合、成膜前に前処理どして光やプラズマ励起されたハ
ロゲンガスにより処理を行う。及び/又は、このガス処
J」に続けて励起された第1のガスによって処理を行う
ことにより基体界面での界面準位密度を低減させるもの
である。[Example] In the present invention, when an insulating film is formed on a semiconductor substrate, pretreatment is performed before film formation using light or plasma-excited halogen gas. and/or the interface state density at the substrate interface is reduced by performing treatment with the excited first gas following this gas treatment.
また、光とプラズマに依る成膜方法を用いることによっ
てハロゲンガス処理を行うに適した低い温度で基体の処
理ができる。加えて前記ハロゲンガスの励起手段として
成膜時に第1のガスを励起するプラズマ源あるいは基体
に照射する光のどちらか一方を用いることによって成膜
装置の簡便化を行うことができる。Furthermore, by using a film forming method that relies on light and plasma, the substrate can be processed at a low temperature suitable for halogen gas processing. In addition, the film forming apparatus can be simplified by using either a plasma source that excites the first gas during film formation or light that irradiates the substrate as means for exciting the halogen gas.
またハロゲンガスによる処理を行う際に光を照射するこ
とによって、水素の脱離が促進され、閾値電極の変動の
原因どなる水素の混入を抑え、緻密な膜を形成すること
が可能となる。また、同様に第1のガスによるガス処理
においても、ガスをプラズマ励起したり、光の照射を行
うことによって、第1ガス種とハロゲン元素どの置換を
効率よく行わせることができる。Furthermore, by irradiating light during the treatment with halogen gas, desorption of hydrogen is promoted, suppressing the incorporation of hydrogen that causes fluctuations in the threshold electrode, and making it possible to form a dense film. Similarly, in the gas treatment using the first gas, the first gas species can be efficiently replaced with the halogen element by plasma excitation of the gas or by irradiation with light.
以下、本発明の薄膜形成法を行うために好適に用いるこ
とができる成膜装置の一例を第1図を用いて説明する。An example of a film forming apparatus that can be suitably used to carry out the thin film forming method of the present invention will be described below with reference to FIG.
第1図において、1は電極であり、2はもう一方の電極
を兼ねている反応容器である。第1図に示されるように
反応容器2は接地されている。In FIG. 1, 1 is an electrode, and 2 is a reaction vessel that also serves as the other electrode. As shown in FIG. 1, the reaction vessel 2 is grounded.
3は基体であり、例えば、シリコンなどの半導体や、G
aAsなとの化合物半導体基体、あるいは絶縁基板上(
絶縁性材料からなる基板あるいは、表面を絶縁状態に成
されている基板)に単結晶Si、多結晶Si、非晶質シ
リコンなどの半導体層を堆積した基体等が挙げられる。3 is a substrate, for example, a semiconductor such as silicon or G
On a compound semiconductor substrate such as aAs or on an insulating substrate (
Examples include a substrate in which a semiconductor layer such as single crystal Si, polycrystalline Si, or amorphous silicon is deposited on a substrate made of an insulating material or a substrate whose surface is in an insulating state.
4a、4b、4cは夫々ガス導入口であり、ガス導入口
4a、4bは、反応容器2の上部に位置しており、電極
Jの近傍に設けである。ガス導入口4aからはハロゲン
元素を含むガス10aを成膜室内に導入し、ガス導入口
4bからは第1のガス10bを導入する。ハロゲン元素
を含むガス10aとしてはHeやArなどの不活性ガス
で希釈したF2.Ca2 、B T 2などのハロゲン
の希釈ガスあるいはHF、l−I Cff、HBr、N
F3、SF6などのハロゲン化合物を含むガスが挙げら
れる。4a, 4b, and 4c are gas inlets, respectively, and the gas inlets 4a, 4b are located in the upper part of the reaction vessel 2, and are provided near the electrode J. A gas 10a containing a halogen element is introduced into the film forming chamber from the gas introduction port 4a, and a first gas 10b is introduced from the gas introduction port 4b. The gas 10a containing a halogen element is F2. diluted with an inert gas such as He or Ar. Diluent gas of halogen such as Ca2, B T2 or HF, l-I Cff, HBr, N
Examples include gases containing halogen compounds such as F3 and SF6.
第1のガスどしては窒素原子を含むガス、酸素原子を含
むガス等があげられる。本発明において、第1のをガス
を使用し前処理を行った場合には、平行平板型プラズマ
CVD法を用いて成膜した場合に比べ、形成される膜中
の水素含有量を格段に低減させることができる。Examples of the first gas include a gas containing nitrogen atoms, a gas containing oxygen atoms, and the like. In the present invention, when the first pretreatment is performed using a gas, the hydrogen content in the formed film is significantly reduced compared to when the film is formed using the parallel plate plasma CVD method. can be done.
ガス導入口4cは電極]と対向した下部側にあり、この
導入[14cから第2のガスlOcが導入される。第2
のガスどしては、Siを含むSiH+ 、Si2H6等
のガスまたはTE01((C2+−+50)、S i)
等の有機オキシシラン材料が挙げられる。The gas introduction port 4c is located on the lower side facing the electrode], and the second gas lOc is introduced from this introduction port [14c]. Second
Examples of the gas include SiH+ containing Si, Si2H6, etc., or TE01 ((C2+-+50), Si)
Organic oxysilane materials such as
5は、反応容器2と電極1との間に電圧を印加し、プラ
ズマを発生さセるための電源である。なおプラズマ発生
手段は、高周波、マイクロ波、マグネットあるいはこれ
らの併用によっても発生さゼることかできる。5 is a power source for applying a voltage between the reaction vessel 2 and the electrode 1 to generate plasma. Note that the plasma generation means can also be generated using high frequency waves, microwaves, magnets, or a combination thereof.
なお、成膜中の反応容器の内部の圧力(操作圧)は10
〜500mTorrどすることが好ましい。The pressure inside the reaction vessel (operating pressure) during film formation was 10
It is preferable to set the temperature to 500 mTorr.
面、上述した薄膜形成方法に43いて、更にプラズマダ
メージを防ぎ、基体の大面積化を図る為には、プラズマ
源の電極面積を、反応容器の内壁面積の1/]○以下に
する事が望ましい。好ましくは、0.02〜0,06で
あl)、より好ましくは0.04〜005である。この
ように電極の面積を反応容器の内壁面積よりも小さくし
、電極と反応容器どの間に電圧を印加すれば、プラズマ
の強度は電極近傍で強く、基体近傍でそれより弱くなり
、その結果、基体または膜へのダメージを軽減すること
ができる。On the other hand, in order to further prevent plasma damage and increase the area of the substrate according to the above-mentioned thin film forming method, it is necessary to make the electrode area of the plasma source less than or equal to 1/]○ of the inner wall area of the reaction vessel. desirable. It is preferably 0.02 to 0.06, more preferably 0.04 to 005. In this way, if the area of the electrode is made smaller than the inner wall area of the reaction vessel and a voltage is applied between the electrode and the reaction vessel, the plasma intensity will be strong near the electrode and weaker near the substrate. Damage to the substrate or film can be reduced.
6は光源であり、例えば、ト1gランプ、Xeランプ、
Xe−トIgランプ、Wランプ、ハロゲンランプ等のラ
ンプ、あるいは、N2レーザ、Arレーザ、Y A G
レーザ、CO2レーザのエギシマレーザ等のレーザがあ
げられる。もちろんこれら以外の光でもよ(、特に導入
ガスに吸収されにくく、成膜時の反応中間体j−3よび
ハロゲンガスに吸収されるものならばよい。尚、ハロゲ
ンガスの励起時に使用する光源やプラズマ源に成膜時の
第1ガス励起のためのプラズマ源あるいは基体に照射コ
1
する光の少なくとも一方を用いる事で装置が簡便どなり
、基体への前処理と成膜プロセスが連続して行える。以
下にこの装置を用いて薄膜形成を行う手順を説明する。6 is a light source, for example, a Tolg lamp, a Xe lamp,
Lamps such as Xe-to-Ig lamps, W lamps, halogen lamps, or N2 lasers, Ar lasers, YAG
Examples include lasers such as lasers, CO2 lasers, and egisimer lasers. Of course, any light other than these may be used as long as it is not easily absorbed by the introduced gas and is absorbed by the reaction intermediate j-3 and the halogen gas during film formation. By using at least one of the plasma source for excitation of the first gas during film formation or the light that irradiates the substrate as a plasma source, the apparatus is simple and the pretreatment of the substrate and the film formation process can be performed continuously. The procedure for forming a thin film using this apparatus will be explained below.
真空容器2内に基体を設置し真空排気装置によって反応
容器2内を所望の圧力まで減圧した後、前処理用ハロゲ
ンガス10 aを導入し操作圧を所望の値に保つ。一方
、この時に光源6から光を基体]に照射するか、電極]
と反応容器2との間に電圧を掛はプラズマ励起するかも
しくはその両方を行う。なお、照射を行う光として赤外
光または赤外光を含む光を用いる場合には、その光照射
により基体の温度を所望の値に設定することができる。After placing the substrate in the vacuum container 2 and reducing the pressure inside the reaction container 2 to a desired pressure using a vacuum evacuation device, a pretreatment halogen gas 10a is introduced to maintain the operating pressure at a desired value. On the other hand, at this time, light is irradiated from the light source 6 onto the substrate or electrodes.
A voltage is applied between the reactor and the reaction vessel 2 to excite the plasma, or to excite the plasma or both. Note that when infrared light or light containing infrared light is used as the light for irradiation, the temperature of the substrate can be set to a desired value by the light irradiation.
また、基体の温度を上昇させることができない光を用い
る場合には、基体支持台にヒーターを設(プて温度を所
望の値に設定しても良い。Furthermore, when using light that cannot raise the temperature of the substrate, a heater may be provided on the substrate support to set the temperature to a desired value.
以上の条件下でハロゲン前処理を行った。その後、反応
容器内を高真空に排気することによってハロゲンガスな
除去する。続いて第1ガスによる処理を行う場合には、
第1ガスどしての酸素や窒素を反応容器内に導入し、操
作圧を所望の値とする。この時もハロゲン前処理の場合
と同じように光源6から光を基体1に照射するか、電極
]と反応容器2との間に電圧を掛しりプラズマ励起する
かもしくはその両方を行うと良い。以上の条件下で第1
ガスによる前処理を行うことができる。Halogen pretreatment was performed under the above conditions. Thereafter, halogen gas is removed by evacuating the inside of the reaction vessel to a high vacuum. When subsequently performing treatment with the first gas,
Oxygen or nitrogen as a first gas is introduced into the reaction vessel and the operating pressure is adjusted to a desired value. At this time, as in the case of halogen pretreatment, it is preferable to irradiate the substrate 1 with light from the light source 6, or to apply a voltage between the electrode and the reaction vessel 2 to excite the plasma, or to perform both. Under the above conditions, the first
Pretreatment with gas can be performed.
次に再び反応容器2内を所望圧まで真空排気する。その
後まず、第1のガスl 01:lをガス導入口4bから
反応容器2の内部に流し、この第1のガスをプラズマ励
起する。第2のガス10cをガス導入口4cから反応容
器2の内部に導入し、ガス圧を所定の値として励起され
た第1のガスと反応を行わせる。プラズマは、例えば1
3.56MHzの高周波電圧を容量結合型電極lと反応
容器2との間に印加することにより発生させることがで
きる。この時に光源から光を基体1に照射し膜形成を行
う。なお、光照射を行うための光源としては前処理時に
用いる光源と異なる光源を用いても良いが、同じ光源と
することによって、装置の簡略化を行うことができる。Next, the inside of the reaction vessel 2 is evacuated to a desired pressure again. After that, first, the first gas l 01:l is flowed into the reaction vessel 2 from the gas inlet 4b, and the first gas is excited into plasma. The second gas 10c is introduced into the reaction vessel 2 through the gas introduction port 4c, and is caused to react with the excited first gas by setting the gas pressure to a predetermined value. For example, plasma is 1
It can be generated by applying a high frequency voltage of 3.56 MHz between the capacitively coupled electrode 1 and the reaction vessel 2. At this time, the substrate 1 is irradiated with light from a light source to form a film. Note that as a light source for performing light irradiation, a light source different from the light source used during pretreatment may be used, but by using the same light source, the apparatus can be simplified.
(実施例1) 以下、本発明の好適な実施例をより具体的に説明する。(Example 1) Hereinafter, preferred embodiments of the present invention will be described in more detail.
反応容器2内に基体どしてSj単結晶ウェハを設置し真
空排気装置に反応容器2内を1×]0Torrまで真空
排気した。その後前処理用ハロゲンガス10aとしてH
eで5%に希釈したF。An Sj single crystal wafer was placed as a substrate in the reaction vessel 2, and the inside of the reaction vessel 2 was evacuated to 1×]0 Torr using a vacuum evacuation device. After that, H is used as the halogen gas 10a for pretreatment.
F diluted to 5% with e.
を5secm導入し操作圧を1. OOm T o r
rに保った。一方、光源6からは0.6W/cITI
’のXeランプ光を基体]に照射した。なお、この照射
により基板温度は300°Cを保ち、以上の条件下で5
分間前処理を行った。was introduced for 5 seconds and the operating pressure was increased to 1. OOm Tor
I kept it at r. On the other hand, from light source 6, 0.6W/cITI
' Xe lamp light was irradiated onto the substrate]. Note that this irradiation keeps the substrate temperature at 300°C, and under the above conditions
Pretreatment was performed for minutes.
次に再び反応容器2内を1×10−T o ’r rま
で真空排気し第1のガス101つとして酸素ガスを用い
、第2のガス10Cどしてモノシランガスを用いた。ま
ず、第1のガス]O]〕をガス導入口41〕から101
005eの割合で反応容器2の内部に流し、この第1の
ガスをプラズマ励起した。第2のガス10cをガス導入
口4cから反応容器2の内部に5secmの割合で導入
しこのときの操作圧を100 m T o r rどし
た。プラズマは、13.56MHzの高周波電圧を容重
結合型電極1ど反応容器2との間に100W印加するこ
とにより発生させた。このときの電子密度は基体3−ヒ
で8X107/cr&であった。 この時も前処理時と
同様に光源6から0 、 6 V+l/ c rdの光
を基体lに照射した。Next, the inside of the reaction vessel 2 was evacuated to 1×10 −T o'r r again, and oxygen gas was used as the first gas 101, and monosilane gas was used as the second gas 10C. First, the first gas [O]] is introduced from the gas inlet 41] to the 101
0.005e into the reaction vessel 2 to excite the first gas into plasma. The second gas 10c was introduced into the reaction vessel 2 from the gas inlet 4c at a rate of 5 seconds, and the operating pressure at this time was 100 mTorr. Plasma was generated by applying a high frequency voltage of 13.56 MHz at 100 W between the capacitively coupled electrode 1 and the reaction vessel 2. The electron density at this time was 8×10 7 /cr& for the substrate 3-H. At this time as well, the substrate 1 was irradiated with light of 0.6 V+l/crd from the light source 6 in the same manner as in the pretreatment.
以上の条件下で3分間堆積を行ったところ]000±2
5人の5iO21]莫が形成された。すなわち、膜厚の
バラツキは約±2.5%ど小さかった。After 3 minutes of deposition under the above conditions] 000±2
Five 5iO21] mos were formed. That is, the variation in film thickness was as small as about ±2.5%.
以上の様にして形成されたシリコン酸化膜の評価を行っ
た。The silicon oxide film formed as described above was evaluated.
■ 屈折率 ]、44〜1.46と熱酸化膜と同程度で
あった。(2) Refractive index] was 44 to 1.46, which was comparable to that of a thermal oxide film.
■ 赤外分光特性 S j −1−1、S −OHの結
合による吸収は見られずS]−〇結合にJこる吸収のみ
であった。(2) Infrared spectral characteristics No absorption due to the S j -1-1, S -OH bond was observed, and only J absorption due to the S]-〇 bond was observed.
■ 電気的特性 比誘電率 4.1、絶縁耐圧10 M
V / c rn、半導体と絶縁膜どの間の界面準位
密度(以下、界面準位密度と称する)5 x 10 ”
e V−’cm
このように良好な特性を持つ膜を形成することができた
。■ Electrical properties Relative dielectric constant 4.1, dielectric strength 10 M
V/crn, interface state density between semiconductor and insulating film (hereinafter referred to as interface state density) 5 x 10"
e V-'cm In this way, a film with good properties could be formed.
[実施例2]
実施例]ど同様に反応容器2内を真空排気した後、l−
1eF25%ガス10aを5secmで導入口4aより
真空反応容器内に導入し、操作圧1、 OOm T o
r rでXeランプを照射し前処理を5分間行った。[Example 2] After evacuating the inside of the reaction vessel 2 in the same manner as in Example], l-
1eF25% gas 10a was introduced into the vacuum reaction vessel from the inlet 4a at 5 sec, and the operating pressure was 1, OOm To
Pretreatment was performed for 5 minutes by irradiating with a Xe lamp at rr.
次に、容器内2を高真空に1ツ1気する事により反応容
器内のF2を除去し、第1のガスである酸素を1010
05e導入して操作圧を1.00 m T o rrど
した。この時も光TA6から0.6W/ci光を照射し
5分間酸素処理を行った。Next, the F2 in the reaction container is removed by applying high vacuum to the container 2 one by one, and the oxygen which is the first gas is
05e was introduced and the operating pressure was increased to 1.00 mTorr. At this time as well, 0.6 W/ci light was irradiated from the light TA6 and oxygen treatment was performed for 5 minutes.
次に第2のガスどしてSjl(45secmをガス導入
口4cから反応容器内に導入し、操作圧を1、 OOm
T o r rとし第1のガスである酸素をプラズマ
により励起した。以−ヒの条件で作成したSin、膜に
ついて堆積速度膜厚分布、屈折率、赤外分光特性、誘電
率、絶縁耐圧は実施例1と同様に良好な結果を示した。Next, the second gas Sjl (45 sec) was introduced into the reaction vessel from the gas inlet 4c, and the operating pressure was set to 1, OOm.
The first gas, oxygen, was excited by plasma. The Sin film prepared under the following conditions showed good results similar to those in Example 1 in terms of deposition rate, film thickness distribution, refractive index, infrared spectral characteristics, dielectric constant, and dielectric strength.
又界面準位密度は2 X 1.0 ”e V−’、cm
−”とさらに小さくなり、酸素処理の効果が確認できた
。Also, the interface state density is 2 x 1.0 "e V-', cm
−”, which confirmed the effect of oxygen treatment.
[実施例3]
実施例]と同様に反応容器内を真空排気した後、HeN
Fs5%ガスを導入口4aより5secmの割合で反応
容器内に導入した後、操作圧を100mTorrとし、
プラズマにより励起した。上記の条件で前処理を5分間
行った。[Example 3] After evacuating the inside of the reaction vessel in the same manner as in Example], HeN
After introducing 5% Fs gas into the reaction vessel from the inlet 4a at a rate of 5 sec, the operating pressure was set to 100 mTorr,
Excited by plasma. Pretreatment was performed for 5 minutes under the above conditions.
その後再び反応容器内を高真空に排気する事により反応
容器内のNF、を除去し、第1のガス(02)を導入口
4]〕から導入し操作圧を]00mTorrとした後、
酸素をプラズマ励起する事により酸素処理を5分間行っ
た。次に第2のガスとしてS I H4をガス導入口4
cから5secmの割合で反応容器内に導入し、操作圧
を100rnTorrとして、第1のガスである酸素を
プラズマにより励起すると同時に光源6より基体上に光
を照I:]する事により成膜した。After that, the NF in the reaction container was removed by evacuating the reaction container to a high vacuum again, and the first gas (02) was introduced from the inlet 4] and the operating pressure was set to ]00 mTorr.
Oxygen treatment was performed for 5 minutes by plasma exciting oxygen. Next, add S I H4 as the second gas to gas inlet 4.
was introduced into the reaction vessel at a rate of 5 sec from C, the operating pressure was set to 100 rnTorr, and the first gas, oxygen, was excited by plasma, and at the same time, light was irradiated onto the substrate from the light source 6 to form a film. .
以上の条件で作成した5jO2膜について堆積速度膜厚
分布、屈折率、赤外分光特性、誘電率、絶縁耐圧は実施
例]と同様に良好な結果を示した。また界面準位密度ば
]、 X ]、 010eV−’cmであった。The 5jO2 film produced under the above conditions showed good results in terms of deposition rate, film thickness distribution, refractive index, infrared spectral characteristics, dielectric constant, and dielectric strength voltage similar to those in Example]. In addition, the interface state density was 010 eV-'cm.
[実施例4〕
実施例1と同様に反応容器2内を真空排気した後、He
NFs5%ガスを導入口4aより5secmの割合で反
応容器内に導入した後、操作圧を100mTorrとし
、プラズマにより励起すると同時に光源6より06W/
ciの光を照射した。その後再び反応容器内を高真空に
排気する事により反応容器内のNF、を除去し、第1の
ガス(0,)を導入口4bから導入し、操作圧を100
mTorrとした。そして酸素をプラズマで励起すると
同時に光源6より基体上に光を照射して、酸素処理を行
った。[Example 4] After evacuating the inside of the reaction vessel 2 in the same manner as in Example 1, He
After introducing 5% NFs gas into the reaction vessel from the inlet 4a at a rate of 5 sec, the operating pressure was set to 100 mTorr, and at the same time the light source 6 was excited at 06 W/
ci light was irradiated. Thereafter, the NF in the reaction container is removed by evacuating the reaction container to high vacuum again, and the first gas (0,) is introduced from the introduction port 4b, and the operating pressure is set to 100.
mTorr. Then, oxygen treatment was performed by exciting oxygen with plasma and simultaneously irradiating light onto the substrate from the light source 6.
次に第2のガスとしてS I H<をガス導入口4cよ
り反応容器内に5secmの割合で導入し、操作圧を1
00mTorrとして、第1のガスである酸素をプラズ
マにより励起すると同時に光源6より基体上に光を照射
する事により成膜を行った。Next, S I H< as the second gas was introduced into the reaction vessel from the gas inlet 4c at a rate of 5 sec, and the operating pressure was increased to 1.
The film was formed by exciting the first gas, oxygen, with plasma and simultaneously irradiating light onto the substrate from the light source 6 at a pressure of 00 mTorr.
以上の条件で作成したSiC2について堆積速度、屈折
率、赤外分光特性、誘電率、絶縁耐圧は実施例1と同様
良好な結果を示した。また界面準位密度は5X 101
1eV−’cm−2と低減することができた。The SiC2 produced under the above conditions showed good results as in Example 1 in terms of deposition rate, refractive index, infrared spectral properties, dielectric constant, and dielectric strength. Also, the interface state density is 5X 101
It was possible to reduce it to 1 eV-'cm-2.
[発明の効果1
本発明によれば、■基体をプラズマの最強部から離して
配置することができるので、基体へのプラズマダメージ
を少なくできる。また励起されたハロゲンガスによる前
処理、且つ/または 励起された第1のガスによる処理
(酸素処理や窒素処理)を行うことによって、界面準位
密度を大幅に減少する事が可能となり、電気的特性に優
れた膜を形成することができる。[Advantageous Effects of the Invention 1] According to the present invention, (1) the substrate can be placed away from the strongest part of the plasma, so that plasma damage to the substrate can be reduced. Furthermore, by performing pretreatment with excited halogen gas and/or treatment with excited first gas (oxygen treatment or nitrogen treatment), it is possible to significantly reduce the interface state density, and the electrical A film with excellent properties can be formed.
■上記ハロゲンガスの励起を、成膜時の第1の反応ガス
の励起のためのに使用するプラズマ源、あるいは基体に
照射を行う光源の少な(とも一方を用いる事で装置が簡
便となり、成膜プロセスが連続して行える。■Excitement of the halogen gas can be achieved by using either a plasma source used to excite the first reaction gas during film formation or a light source that irradiates the substrate (using either one simplifies the equipment and Membrane process can be performed continuously.
■化学量論組成から近い膜を形成することができる。■A film with a close stoichiometric composition can be formed.
■水素含有量の少ない膜を形成でき、閾値電圧の変動を
抑えることができる。■It is possible to form a film with low hydrogen content, and it is possible to suppress fluctuations in threshold voltage.
第1図は本発明の実施例に係る装置を示す概念図である
。
]・・・電極、2・・・反応容器、
3・・・基体、
4a、4b、4cm ・・ガス導入口、5・・・プラズ
マ発生手段、
6・・・光源、FIG. 1 is a conceptual diagram showing an apparatus according to an embodiment of the present invention. ]...Electrode, 2...Reaction container, 3...Substrate, 4a, 4b, 4cm...Gas inlet, 5...Plasma generation means, 6...Light source,
Claims (1)
、 基体の配された成膜室内にハロゲンガスを導入する工程
と、 前記ハロゲンガスを励起し前記基体を処理するハロゲン
処理工程と、 前記ハロゲン処理後、励起しても単独では堆積しない第
1のガスを基体の配された反応容器内に導入する工程と
、 前記反応容器内に導入された前記第1のガスをプラズマ
励起する工程と、 第2のガスを前記反応容器内に導入し、前記励起された
第1のガスと反応させ、生成した反応生成物を基体上に
付着せしめ、前記反応生成物が付着する基体に光を照射
する工程とを有することを特徴とする薄膜形成方法。 2、プラズマと光を用いて成膜を行う成膜方法において
、 基体の配された成膜室内にハロゲンガスを導入する工程
と、 前記ハロゲンガスを励起し前記基体を処理するハロゲン
処理工程と、 前記ハロゲン処理後、励起しても単独では堆積しない第
1のガスを基体の配された反応容器内に導入する工程と
、 前記反応容器内に導入された前記第1のガスをプラズマ
励起する工程と、 前記ハロゲン処理後の基体を励起された前記第1のガス
にさらす工程と、 第2のガスを前記反応容器内に導入し、前記励起された
第1のガスと反応させ、生成した反応生成物を基体上に
付着せしめ、前記反応生成物が付着する基体に光を照射
する工程とを有することを特徴とする薄膜形成方法。[Scope of Claims] 1. In a film formation method using plasma and light, the steps include: introducing a halogen gas into a film formation chamber in which a substrate is arranged; and exciting the halogen gas to treat the substrate. a step of introducing a first gas that does not deposit on its own even when excited after the halogen treatment into a reaction vessel in which a substrate is arranged; a step of plasma-exciting a gas; introducing a second gas into the reaction vessel and reacting with the excited first gas, depositing a generated reaction product on a substrate; A method for forming a thin film, comprising the step of irradiating light onto a substrate to which it is attached. 2. In a film formation method using plasma and light, the steps include: introducing a halogen gas into a film formation chamber in which a substrate is arranged; a halogen treatment step of exciting the halogen gas and treating the substrate; After the halogen treatment, a step of introducing a first gas that does not deposit on its own even when excited into a reaction container in which a substrate is arranged; and a step of plasma exciting the first gas introduced into the reaction container. a step of exposing the substrate after the halogen treatment to the excited first gas; and introducing a second gas into the reaction vessel and reacting with the excited first gas, resulting in a reaction. A method for forming a thin film, comprising the steps of: depositing a product on a substrate; and irradiating the substrate to which the reaction product is deposited with light.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP22967890A JPH04110471A (en) | 1990-08-30 | 1990-08-30 | Formation of thin film |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP22967890A JPH04110471A (en) | 1990-08-30 | 1990-08-30 | Formation of thin film |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH04110471A true JPH04110471A (en) | 1992-04-10 |
Family
ID=16895977
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP22967890A Pending JPH04110471A (en) | 1990-08-30 | 1990-08-30 | Formation of thin film |
Country Status (1)
Country | Link |
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JP (1) | JPH04110471A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07235530A (en) * | 1994-02-24 | 1995-09-05 | G T C:Kk | Formation of insulating film |
US7465679B1 (en) | 1993-02-19 | 2008-12-16 | Semiconductor Energy Laboratory Co., Ltd. | Insulating film and method of producing semiconductor device |
-
1990
- 1990-08-30 JP JP22967890A patent/JPH04110471A/en active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7465679B1 (en) | 1993-02-19 | 2008-12-16 | Semiconductor Energy Laboratory Co., Ltd. | Insulating film and method of producing semiconductor device |
JPH07235530A (en) * | 1994-02-24 | 1995-09-05 | G T C:Kk | Formation of insulating film |
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