JPH0242725A - Manufacture of semiconductor device - Google Patents
Manufacture of semiconductor deviceInfo
- Publication number
- JPH0242725A JPH0242725A JP19271688A JP19271688A JPH0242725A JP H0242725 A JPH0242725 A JP H0242725A JP 19271688 A JP19271688 A JP 19271688A JP 19271688 A JP19271688 A JP 19271688A JP H0242725 A JPH0242725 A JP H0242725A
- Authority
- JP
- Japan
- Prior art keywords
- semiconductor device
- manufacturing
- gas
- oxide film
- substrate
- 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 17
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 238000000034 method Methods 0.000 claims abstract description 35
- 230000003647 oxidation Effects 0.000 claims abstract description 28
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 28
- 239000000758 substrate Substances 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- 125000005843 halogen group Chemical group 0.000 claims abstract description 13
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 8
- 230000001698 pyrogenic effect Effects 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 8
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims 3
- 238000001035 drying Methods 0.000 claims 2
- 229910052731 fluorine Inorganic materials 0.000 abstract description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 19
- 238000002347 injection Methods 0.000 abstract description 11
- 239000007924 injection Substances 0.000 abstract description 11
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 8
- 239000000377 silicon dioxide Substances 0.000 abstract description 8
- 229910052736 halogen Inorganic materials 0.000 abstract description 7
- 150000002367 halogens Chemical class 0.000 abstract description 7
- 229910052681 coesite Inorganic materials 0.000 abstract description 6
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 6
- 229910052682 stishovite Inorganic materials 0.000 abstract description 6
- 229910052905 tridymite Inorganic materials 0.000 abstract description 6
- 230000007423 decrease Effects 0.000 abstract description 3
- 229910052814 silicon oxide Inorganic materials 0.000 abstract description 3
- 238000010894 electron beam technology Methods 0.000 abstract description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 18
- 239000011737 fluorine Substances 0.000 description 18
- 230000000694 effects Effects 0.000 description 13
- 238000009279 wet oxidation reaction Methods 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 7
- 238000007796 conventional method Methods 0.000 description 5
- 230000005855 radiation Effects 0.000 description 5
- 239000003990 capacitor Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000002955 isolation Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
Landscapes
- Formation Of Insulating Films (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は高集積微細ＭＯＳデバイスの製造方法に係り、
特に耐放射線、耐ホツトキャリア現象に対して優れた半
導体装置の製造方法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method of manufacturing a highly integrated fine MOS device,
In particular, the present invention relates to a method of manufacturing a semiconductor device that is excellent in radiation resistance and hot carrier phenomenon resistance.
従来の報告例によれば、耐放射線特性、耐ホツトキャリ
ア特性の優れたゲート絶縁膜が、常圧下での乾燥酸化中
あるいは酸化前のＳｉの表面にＦ又はＣｌを適当な量導
入することによって得られることが示されている。According to conventional reports, a gate insulating film with excellent radiation resistance and hot carrier resistance can be obtained by introducing an appropriate amount of F or Cl into the Si surface during or before dry oxidation under normal pressure. It has been shown that it can be obtained.
これらの報告の例としては１例えば、アイ・イー・イー
・イー、エレクトロンデバイス レター第９巻（１９８
８年）第３８頁から４０頁（ＩＥ［１ＥＩＥｌｅｃｔｒ
ｏｎ Ｄｅｖｉｃｅ Ｌｅｔｔｅｒ、 ＥＤＬ−９（１
９８８）。Examples of these reports include 1, for example, IEE, Electron Device Letters Volume 9 (198
8th year) pages 38 to 40 (IE[1EIElectr
on Device Letter, EDL-9 (1
988).
ｐｐ３８−４０）において論じられている。pp 38-40).
上記従来技術はｌＭＯＳトランジスタのゲート絶縁膜の
信頼性向上を目的としている。したかつ＼
１て、酸化膜は乾燥（ドライ）酸化法によって形成され
た５００Å以下の簿膜であって、ＭＯＳデバイスのアイ
ソレーション等で必要とされる５０００人−１μｍ程度
の厚膜を形成できる水蒸気中での酸化（ウェット）法に
ついてハロゲンの効果については配慮されていなかった
。The purpose of the above-mentioned conventional technology is to improve the reliability of the gate insulating film of an IMOS transistor. First, the oxide film is a film with a thickness of 500 Å or less formed by a dry oxidation method, and it is possible to form a thick film of about 5000-1 μm, which is required for isolation of MOS devices, etc. Regarding the oxidation (wet) method in water vapor, no consideration was given to the effect of halogens.
Ｓｉデバイスにおいては浅接合化が必要であるが、その
さい、Ｓｉデバイスの製造工程における熱処理温度を低
く抑えることも重要になってきた。In Si devices, shallower junctions are required, and at this time, it has become important to keep the heat treatment temperature low in the Si device manufacturing process.
従来の大気圧中の酸化法に比べて、高圧の酸素ガス中で
酸化することにより、酸化速度を増大させる方法（高圧
酸化法）がある。この高圧酸化方法によって、低温でも
ＭＯＳデバイスの実現に必要な酸化膜厚を得ることがで
きる。Compared to the conventional oxidation method at atmospheric pressure, there is a method (high-pressure oxidation method) in which the oxidation rate is increased by oxidizing in high-pressure oxygen gas. This high-pressure oxidation method makes it possible to obtain the oxide film thickness necessary to realize a MOS device even at low temperatures.
この高圧酸化法におけるハロゲンの効果についても配慮
されていなかった。No consideration was given to the effect of halogen in this high-pressure oxidation method.
本発明の目的は、ＭＯＳデバイス中等のアイソレーショ
ン等で必要とされる高信頼性のウェット酸化膜や低温で
形成できる高圧酸化膜を製造することにある。An object of the present invention is to manufacture a highly reliable wet oxide film required for isolation of MOS devices, etc., and a high-pressure oxide film that can be formed at low temperatures.
上記目的は、ウェット酸化膜または高圧酸化膜と基板Ｓ
ｉとの界面に微量のハロゲンを８人することにより、達
成される。The above purpose is to combine wet oxide film or high pressure oxide film with substrate S.
This is achieved by adding a small amount of halogen to the interface with i.
絶縁膜とＳｉとの界面の信頼性は、この絶縁膜（通常は
５ｉＯｚ）とＳｉの結合の格子不整合による歪に大きく
依存すると考えられる。この歪を持つ界面での５ｉ−０
結合は、放射線ダメージ。The reliability of the interface between the insulating film and Si is considered to be largely dependent on the strain caused by the lattice mismatch in the bond between the insulating film (usually 5 iOz) and Si. 5i-0 at the interface with this strain
The bond is radiation damage.
ホットキャリア注入で生ずる欠陥の該Ｓｉ／ＳｉＯ２界
面に拡散により切断される。この切断された結合によっ
て、界面準位、固定電荷トラップ中心などが形成される
ことが知られている。これに対して、Ｓｉと結合力の強
いＦ、ＣＩ２などのハロゲン元素をＳｉ／ＳｉＯｘ界面
に適当な量導入することによって、この界面での歪を緩
和することができ、これによって高信頼のＳｉ／ＳｉＯ
ｘ界面を形成できると考えられる。Defects caused by hot carrier injection are cut at the Si/SiO2 interface by diffusion. It is known that interface states, fixed charge trap centers, and the like are formed by these broken bonds. On the other hand, by introducing an appropriate amount of halogen elements such as F and CI2, which have a strong bonding force with Si, into the Si/SiOx interface, the strain at this interface can be alleviated. /SiO
It is thought that an x-interface can be formed.
本発明によって、ドライ酸化膜が確かめられていた、ハ
ロゲン導入によるＳ ｉ ／ Ｓ ｉ Ｏ２の信頼性の
向上が、ウェット酸化法によって形成されたＳｉ／Ｓｉ
Ｏｘの界面においても同様に起こることが明らかになっ
た。According to the present invention, the reliability improvement of Si/SiO2 due to the introduction of halogen, which has been confirmed in dry oxide films, has been confirmed to be improved by Si/SiO2 formed by wet oxidation method.
It has become clear that the same phenomenon occurs at the Ox interface.
以下、実施例によって、本発明の概念を詳細に説明する
。Hereinafter, the concept of the present invention will be explained in detail with reference to Examples.
（実施例１）
本実施例においては、本発明の効果を明確に示すために
、従来法を用いて形成した酸化膜と本発明を用いた絶縁
膜とを形成して、キャパシタを作り、耐ホツトキャリア
特性を調べた。(Example 1) In this example, in order to clearly demonstrate the effects of the present invention, a capacitor was fabricated by forming an oxide film formed using a conventional method and an insulating film using the present invention. The hot carrier properties were investigated.
従来技術を用いたＭＯＳキャパシタは例えば、Ｓｉ基板
の洗浄後に１０００℃の乾燥酸素中で約５０分酸化して
約５００人のドライ酸化膜を形成したのち、１０００℃
の水蒸気を含む酸素中で約３０分酸化して合計約５００
０人の酸化膜を形成した。For example, in a MOS capacitor using the conventional technology, after cleaning the Si substrate, oxidize it for about 50 minutes in dry oxygen at 1000°C to form a dry oxide film of about 500%, and then oxidize it at 1000°C.
Oxidized for about 30 minutes in oxygen containing water vapor to give a total of about 500
An oxide film of 0 people was formed.
一方、本発明の方法を用いたＭＯＳキャパシタは、Ｓｉ
基板の洗浄後に、この基板を２．５％の弗化水素酸の水
溶液に約５分間侵し、そのまま乾燥させる。そのさい、
このＳｉ基板の表面には、多量の弗素が吸着されている
。このＳｉ基板を１０００℃の乾燥雰囲気で５０分間酸
化して５００人の酸化膜を形成する。さらに、この５０
０人の弗素を導入したドライ酸化膜を１０００℃の水蒸
気を含む酸素中で約３０分酸化することによって合計約
５０００人の膜厚の酸化膜を形成する。On the other hand, a MOS capacitor using the method of the present invention is made of Si
After cleaning the substrate, the substrate is soaked in a 2.5% aqueous solution of hydrofluoric acid for about 5 minutes and then allowed to dry. At that time,
A large amount of fluorine is adsorbed on the surface of this Si substrate. This Si substrate is oxidized for 50 minutes in a dry atmosphere at 1000° C. to form a 500-layer oxide film. Furthermore, this 50
A dry oxide film into which 0 fluorine was introduced was oxidized for about 30 minutes in oxygen containing water vapor at 1000° C. to form an oxide film with a total thickness of about 5000 fluorine.
上記の方法によって
ｉ）通常のドライ酸化膜５００人
ｉｉ）ドライ＋ウェット酸化膜５０００人１ｉｉ）ウェ
ット酸化膜５０００人
ｉｙ）フッ素を含むドライ酸化膜５００人Ｖ）フッ素を
含むドライ＋ウェット酸化膜５０００人
の５種類の膜を形成して、この絶縁膜（ＳｉＯ２）上に
ＡＱ組電極形成してキャパシタを作成し、そのホットキ
ャリア注入による界面準位の発生量を比較した。By the above method, i) Normal dry oxide film 500 people ii) Dry + wet oxide film 5000 people 1ii) Wet oxide film 5000 people iy) Dry oxide film containing fluorine 500 people V) Dry + wet oxide film containing fluorine 5000 people Five types of films were formed, and a capacitor was created by forming an AQ electrode set on the insulating film (SiO2), and the amount of interface states generated by hot carrier injection was compared.
ホットキャリア注入は、Ｓｉ基板から酸化膜中に電子を
注入するＦ−Ｎトンネル法で行った。電流密度は６ ｘ
１０””Ａ／ｃｉで、注入時間は２００秒である。界
面準位の測定は、高周波（Ｉ Ｍ Ｈｚ ）と準静的容
量−電圧測定により行った。Hot carrier injection was performed using the F-N tunneling method in which electrons are injected from the Si substrate into the oxide film. Current density is 6 x
At 10''A/ci, the injection time is 200 seconds. The interface state was measured by high frequency (I MHz) and quasi-static capacitance-voltage measurements.
第１図に、ホットキャリア注入後に発生した界面準位密
度のＳｉのバンドキャップ中での分布を、比較して示す
。第１図の１は弗素を含まない５００人の膜厚のドライ
酸化膜、２は弗素を含まない５０００人の膜厚のドライ
＋ウェット酸化膜、３は弗素を含まない５０００人のウ
ェット酸化膜、４は弗素を含む５００人のドライ酸化膜
、５は本発明の実施例の弗素を含む５００人の膜厚のド
ライ＋ウェット酸化膜をそれぞれ示す。FIG. 1 shows a comparative distribution of the interface state density generated after hot carrier injection in the Si band gap. In Figure 1, 1 is a 500-layer dry oxide film that does not contain fluorine, 2 is a 5000-layer dry + wet oxide film that does not contain fluorine, and 3 is a 5000-layer wet oxide film that does not contain fluorine. , 4 shows a 500-thick dry oxide film containing fluorine, and 5 shows a 500-thick dry+wet oxide film containing fluorine according to an embodiment of the present invention.
１と４を比較するとすでに知られているように、弗素を
含むドライ酸化膜の界面準位の発生量が、弗素を含まな
いドライ酸化膜の約１／１ｏになっている。５の弗素を
含むドライ＋ウェット酸化膜は、４の弗素を含むドライ
酸化膜に比べて、やや界面準位の量が多くなっているが
、これは、ウェット酸化によって、酸化膜中に水素や水
酸基が導入されたためと考えられる。しかし、２，３の
ドライ＋ウェット酸化膜、ウェット酸化膜に比較すると
本発明の方法によって形成した。５の酸化膜の信頼性の
高さが極めて著るしいことが明らかとなる。Comparing No. 1 and No. 4, as already known, the amount of interface states generated in a dry oxide film containing fluorine is about 1/1 of that of a dry oxide film not containing fluorine. The dry + wet oxide film containing fluorine in No. 5 has a slightly larger amount of interface states than the dry oxide film containing fluorine in No. 4, but this is because wet oxidation causes hydrogen and wet oxide in the oxide film. This is thought to be due to the introduction of hydroxyl groups. However, compared to the dry+wet oxide films and wet oxide films of 2 and 3, the results were formed by the method of the present invention. It is clear that the reliability of the oxide film No. 5 is extremely high.
なお、本実施例において、ドライ酸化＋ウェット酸化と
いうやや複雑な酸化工程を用いたが、このドライ酸化工
程を省略して、直接ウェット酸化中に弗素を導入しても
、まったく同等の効果が得られた。このドライ＋ウェッ
ト法によって本発明を応用するさいには、通常ゲート絶
縁膜として用いる薄いドライ酸化膜にも弗素を導入する
ことによって、高信頼性のデバイスが形成できるためで
ある。In this example, a somewhat complicated oxidation process of dry oxidation + wet oxidation was used, but even if this dry oxidation process was omitted and fluorine was directly introduced during wet oxidation, exactly the same effect could be obtained. It was done. This is because when the present invention is applied by this dry+wet method, a highly reliable device can be formed by introducing fluorine into a thin dry oxide film normally used as a gate insulating film.
（実施例２）
上記の実施例１に比べてさらに制御性の良いＦの酸化膜
中への導入法の一つにＮＦａ酸化法がある。(Example 2) One of the methods for introducing F into the oxide film with better controllability than in Example 1 is the NFa oxidation method.
この方法において、ウェット酸化の初期にＮ Ｆ ａガ
スの０２中での濃度が０．０５％ となるようにして、
流し、このＮ Ｆ ａガスの４入を行なっている時間を
変えて、酸化膜中のＦの量を調節した。In this method, the concentration of NFa gas in O2 is set to 0.05% at the initial stage of wet oxidation,
The amount of F in the oxide film was adjusted by changing the time during which the NFa gas was introduced into the oxide film.
第２図は、ホットキャリア注入によって発生した界面準
位の密度（ミツドギャップより高エネルギー側にあるピ
ークの高さ）を、ＮＦａガス導入時間の関数として示し
たものである。界面準位密度は、ＮＦａ導入時間が１０
０秒以下で著しく減少する。また、この界面準位の少な
い領域は、ＮＦ３ガス感度（％）とＮＦａ導入時間の積
が５％Ｘ秒以下に現れることがさらに一般的に明らかと
なった。FIG. 2 shows the density of interface states (the height of the peak on the higher energy side than the mid-gap) generated by hot carrier injection as a function of the NFa gas introduction time. The interface state density is determined by the NFa introduction time of 10
It decreases significantly in less than 0 seconds. Furthermore, it has become more generally clear that this region with few interface states appears when the product of NF3 gas sensitivity (%) and NFa introduction time is 5%X seconds or less.
本実施例では、ＮＦａは、ウェット酸化中に導入したが
、このＮ Ｆ ｓはドライ酸化中に導入して、さらにウ
ェット酸化工程を導入してもまったく同等の効果が得ら
れる。In this example, NFa was introduced during wet oxidation, but the same effect can be obtained by introducing N F s during dry oxidation and then further introducing a wet oxidation step.
上記の２つの実施例１と２において、酸化膜中にＦを導
入する方法について述べたが、はとんど同等な効果が塩
素（Ｃｌ）を導入することによっても得られた。以下、
ＷＮ単に説明する。In the above two Examples 1 and 2, the method of introducing F into the oxide film was described, but almost the same effect was obtained by introducing chlorine (Cl). below,
WN I will simply explain.
ウェットあるいは、ドライ酸化中にトリクロルエタンＣ
ｘＨｓＣｌａ（通称ＴＣＡ）を導入するさいには、０２
中のＴＣＡの濃度と導入時間との積が。Trichloroethane C during wet or dry oxidation
When introducing xHsCla (commonly known as TCA), 02
The product of the concentration of TCA in the medium and the introduction time.
１０００℃の酸化温度においては、３０％・秒以下で界
面準位の著しい減少が認められた。At an oxidation temperature of 1000° C., a significant decrease in interface states was observed within 30%·sec.
また、ＨＣｌガス導入によってＣｌを酸化膜中に導入す
るさいには、０２中のＨＣｌの濃度とこのＨＣｌガスの
酸化炉中への導入時間との積が１０％・秒以下とするこ
とによって著しい界面準位の低下が実現する。なお１本
実施例中で示した酸化は大気圧下で行った。In addition, when introducing Cl into the oxide film by introducing HCl gas, it is possible to make a significant A reduction in the interface state is achieved. Note that the oxidation shown in this example was performed under atmospheric pressure.
また、本実施例と同様な効果は、Ｆ、Ｃｌの代りに同じ
ハロゲン族のＢｒ、Ｉを用いても期待できる。Further, the same effect as in this example can be expected even if Br and I of the same halogen group are used instead of F and Cl.
なお１本発明によって、界面準位の減少効果のみではな
く、さらに、絶縁膜中の固定電荷も少なくすることがで
きた。Note that according to the present invention, not only the interface state can be reduced, but also fixed charges in the insulating film can be reduced.
また、本実施例において、ホットキャリア法によって５
ｉＯｚ／Ｓｉ 系の信頼性の評価を行ったが、まった
く同等な効果が、Ｘ線、電子線照射による界面準位の発
生過程においても確認された。In addition, in this example, 5
The reliability of the iOz/Si 2 system was evaluated, and exactly the same effect was confirmed in the generation process of interface states by X-ray and electron beam irradiation.
また１本実施例において、ウェット酸化は水蒸気を含む
酸素による酸化法を用いた結果を示したが、本発明の実
施例とまったく同等の効果が、Ｈ２と０２を酸化炉に導
入して酸化を行なうパイロジェニック酸化法においても
確認された。In addition, in this example, wet oxidation was performed using an oxidation method using oxygen containing water vapor, but the same effect as in the example of the present invention can be obtained by introducing H2 and 02 into the oxidation furnace. It was also confirmed in the pyrogenic oxidation method.
（実施例３）
上記のウェット酸化膜にＦ、Ｃｌを導入する方法に加え
て、ここでは、乾燥酸素中で行なうシリコンの高圧酸化
においても実施例１，２と同様な改善効果があったので
照合する。(Example 3) In addition to the above-mentioned method of introducing F and Cl into the wet oxide film, the same improvement effect as in Examples 1 and 2 was obtained by high-pressure oxidation of silicon in dry oxygen. Verify.
本発明の方法を用いたＭＯＳゲート酸化膜は。A MOS gate oxide film using the method of the present invention is as follows.
Ｓｉ基板の洗浄後に、この基板を２．５％の弗化水素酸
の水溶液に約５分間侵し、そのまま乾燥させた。この基
板を８５０℃の高圧酸素雰囲気（４−７気圧）中で酸化
した。この方法によって、約２０ｎｍ−５０ｎｍの膜厚
の酸化膜が形成された。After cleaning the Si substrate, the substrate was immersed in a 2.5% aqueous solution of hydrofluoric acid for about 5 minutes and then allowed to dry. This substrate was oxidized in a high pressure oxygen atmosphere (4-7 atm) at 850°C. By this method, an oxide film with a thickness of approximately 20 nm to 50 nm was formed.
この方法によって形成した酸化膜のホットキャリア注入
または放射線照射による界面準位の発生量は、従来の高
圧酸化膜に比べて約１／１０以下であった。The amount of interface states generated by hot carrier injection or radiation irradiation in the oxide film formed by this method was about 1/10 or less compared to a conventional high-pressure oxide film.
これと同様な高圧酸化膜の改善効果は、実施例１と２に
示した。Ｆ、Ｃｌの導入条件下でも得られた。Similar improvement effects of the high-pressure oxide film were shown in Examples 1 and 2. It was also obtained under conditions where F and Cl were introduced.
本発明によれば、アイソレーション等に用いられる厚い
２酸化シリコン中の界面準位の発生量を従来法によって
形成した２酸化シリコンの１／１０程度以下ば減らすこ
とができる。これによって、酸化シリコンとＳｉの界面
に発生する界面準位、固定電荷によって生ずる表面リー
クを防ぎ。According to the present invention, the amount of interface states generated in thick silicon dioxide used for isolation etc. can be reduced to about 1/10 of that of silicon dioxide formed by conventional methods. This prevents surface leakage caused by interface states and fixed charges generated at the interface between silicon oxide and Si.
高信頼性（例えば、Ｘｉ、 ｆＩｉ子線などによるラジ
エーション、ホットキャリヤ注入に対する）のＭＯＳデ
バイスを形成できる。A highly reliable MOS device (for example, against radiation caused by Xi, fIi, etc., and hot carrier injection) can be formed.
第１図は、本発明の一実施例と従来例におけるホットキ
ャリア注入によって発生した界面準位のエネルギー分布
を示す図、第２図は、ホットキャリア注入によって発生
した界面準位密度のＮ Ｆ ａガス導入時間依存性を示
す図である。
１・・・従来法によるドライ酸化膜、２・・・従来法に
よるドライ＋ウェット酸化膜、３・・・従来法によるウ
ェット酸化膜、４・・・弗素を含むドライ酸化膜、５・
・・弗素を含むドライ＋ウェット酸化膜（本発明）。
鴇
口
Ｂ−Ｅη＜ｅｖ）
第
図
Ｆｌ
導入時間（＃）FIG. 1 is a diagram showing the energy distribution of interface states generated by hot carrier injection in an embodiment of the present invention and a conventional example, and FIG. 2 is a diagram showing the energy distribution of interface states generated by hot carrier injection. It is a figure showing gas introduction time dependence. 1... Dry oxide film by conventional method, 2... Dry+wet oxide film by conventional method, 3... Wet oxide film by conventional method, 4... Dry oxide film containing fluorine, 5...
...Dry + wet oxide film containing fluorine (this invention). Tokiguchi B-Eη<ev) Figure Fl Introduction time (#)
Claims (1)
て形成されたＳｉＯ＿２との界面に含む半導体装置を、
水蒸気を含む酸素雰囲気中または、パイロジエニツク雰
囲気中、または高圧の酸素中で酸化することを特徴とす
る半導体装置の製造方法。 ２、上記の半導体装置の製造方法において、ハロゲン原
子はＦであり、該Ｆ原子は、上記乾式酸化の前に上記Ｓ
ｉ基板を弗化水素酸の水溶液を塗布し乾燥させた後に、
乾燥酸素雰囲気中で該Ｓｉ基板を酸化することにより導
入することを特徴とする請求項第１項記載の半導体装置
の製造方法。 ３、上記の半導体装置の製造方法において、ハロゲン原
子はＦであり、該Ｆ原子は、上記乾燥酸化中に、ＮＦ＿
３ガスのＯ＿２ガス中での濃度（％）と該ＮＦ＿３ガス
の導入時間の積が、５％・秒以下の条件で導入されるこ
とを特徴とする請求項第１項記載の半導体装置の製造方
法。 ４、上記の半導体装置の製造方法において、ハロゲン原
子はＣｌであり、上記乾式酸化中に、トリクロルエタン
（ＴＣＡ）ガスのＯ＿２ガス中の濃度と該ＴＣＡガスの
導入時間の積が、３０％・秒以下で導入することを特徴
とする請求項第１項記載の半導体装置の製造方法。 ５、ハロゲン原子はＣｌであり、上記乾燥酸化中に、Ｏ
＿２ガス中ＨＣｌの濃度と該ＨＣｌの導入時間の積が１
０％・秒以下であることを特徴とする請求項第１項記載
の半導体装置の製造方法。 ６、Ｓｉ基板を酸化する前の該Ｓｉ基板の表面にハロゲ
ン原子を吸着させるか、もしくは、酸化中に微量のハロ
ゲン原子を酸化炉中に導入し、該Ｓｉ基板を水蒸気を含
む酸素雰囲気中又は、パイロジエニツク雰囲気中で酸化
することを特徴とする半導体装置の製造方法。 ７、上記ハロゲン原子はＦであり、該Ｆ原子はＳｉ基板
表面に弗化水素酸の水溶液を塗布し、乾燥させることに
より吸着させることを特徴とする請求項第６項記載の半
導体装置の製造方法。 ８、上記ハロゲン原子はＦであり、該Ｆ原子量は、上記
の水蒸気を含む酸素中のＮＦ＿３ガス濃度（％）と導入
時間の積が５％・秒以下であることを特徴とする請求項
第６項記載の半導体装置の製造方法。 ９、上記ハロゲン原子はＣｌであり、上記の水蒸気を含
む酸素中に、トリクロルエタン（ＴＣＡ）ガスのＯ＿２
ガス中での濃度と該ＴＣＡガスの導入時間との積が３０
％・秒以下で導入することを特徴とする請求項第６項記
載の半導体装置の製造方法。 １０、上記ハロゲン原子はＣｌであり、上記の水蒸気を
含む酸素中に、Ｏ＿２ガス中のＨＣｌ濃度（％）と該Ｈ
Ｃｌの導入時間との積が１０％・秒以下であることを特
徴とする請求項第６項記載の半導体装置の製造方法。[Claims] 1. A semiconductor device containing a trace amount of halogen atoms at the interface with SiO_2 formed by dry oxidation of a Si substrate,
A method for manufacturing a semiconductor device, characterized in that oxidation is carried out in an oxygen atmosphere containing water vapor, in a pyrogenic atmosphere, or in high-pressure oxygen. 2. In the above method for manufacturing a semiconductor device, the halogen atom is F, and the F atom is added to the S before the dry oxidation.
After applying an aqueous solution of hydrofluoric acid to the i-board and drying it,
2. The method of manufacturing a semiconductor device according to claim 1, wherein the introduction is performed by oxidizing the Si substrate in a dry oxygen atmosphere. 3. In the above method for manufacturing a semiconductor device, the halogen atom is F, and the F atom is converted into NF_
2. Manufacturing the semiconductor device according to claim 1, wherein the product of the concentration (%) of the three gases in O_2 gas and the introduction time of the NF_3 gas is 5% seconds or less. Method. 4. In the above method for manufacturing a semiconductor device, the halogen atom is Cl, and during the dry oxidation, the product of the concentration of trichloroethane (TCA) gas in O_2 gas and the introduction time of the TCA gas is 30%. 2. The method of manufacturing a semiconductor device according to claim 1, wherein the introduction is performed in seconds or less. 5. The halogen atom is Cl, and during the above dry oxidation, O
_2 The product of the concentration of HCl in the gas and the introduction time of the HCl is 1
2. The method of manufacturing a semiconductor device according to claim 1, wherein the time is 0%·sec or less. 6. Adsorb halogen atoms onto the surface of the Si substrate before oxidizing the Si substrate, or introduce a trace amount of halogen atoms into an oxidation furnace during oxidation, and place the Si substrate in an oxygen atmosphere containing water vapor or , a method for manufacturing a semiconductor device characterized by oxidizing it in a pyrogenic atmosphere. 7. Manufacturing the semiconductor device according to claim 6, wherein the halogen atom is F, and the F atom is adsorbed by applying an aqueous solution of hydrofluoric acid to the surface of the Si substrate and drying it. Method. 8. The halogen atom is F, and the atomic weight of F is such that the product of the NF_3 gas concentration (%) in the water vapor-containing oxygen and the introduction time is 5% seconds or less. 6. A method for manufacturing a semiconductor device according to item 6. 9. The halogen atom is Cl, and O_2 of trichloroethane (TCA) gas is added to the oxygen containing water vapor.
The product of the concentration in the gas and the introduction time of the TCA gas is 30
7. The method of manufacturing a semiconductor device according to claim 6, wherein the introduction is performed at a rate of less than %.sec. 10. The above halogen atom is Cl, and in the above oxygen containing water vapor, the HCl concentration (%) in O_2 gas and the H
7. The method of manufacturing a semiconductor device according to claim 6, wherein the product with the introduction time of Cl is 10%·sec or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19271688A JPH0242725A (en) | 1988-08-03 | 1988-08-03 | Manufacture of semiconductor device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19271688A JPH0242725A (en) | 1988-08-03 | 1988-08-03 | Manufacture of semiconductor device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0242725A true JPH0242725A (en) | 1990-02-13 |
Family
ID=16295872
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19271688A Pending JPH0242725A (en) | 1988-08-03 | 1988-08-03 | Manufacture of semiconductor device |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0242725A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0428265A (en) * | 1990-05-23 | 1992-01-30 | Seiko Instr Inc | Semiconductor device and manufacture thereof |
| JPH0456223A (en) * | 1990-06-25 | 1992-02-24 | Matsushita Electron Corp | Formation of silicon oxide film and thin film formation device |
| US5846888A (en) * | 1996-09-27 | 1998-12-08 | Micron Technology, Inc. | Method for in-situ incorporation of desirable impurities into high pressure oxides |
| JP2000012864A (en) * | 1998-06-22 | 2000-01-14 | Semiconductor Energy Lab Co Ltd | Manufacture of semiconductor device |
| JP2007158371A (en) * | 2007-02-02 | 2007-06-21 | Semiconductor Energy Lab Co Ltd | Method of manufacturing semiconductor device |
| JP2014103175A (en) * | 2012-11-16 | 2014-06-05 | Fuji Electric Co Ltd | Silicon carbide semiconductor device and silicon carbide semiconductor device manufacturing method |
-
1988
- 1988-08-03 JP JP19271688A patent/JPH0242725A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0428265A (en) * | 1990-05-23 | 1992-01-30 | Seiko Instr Inc | Semiconductor device and manufacture thereof |
| JPH0456223A (en) * | 1990-06-25 | 1992-02-24 | Matsushita Electron Corp | Formation of silicon oxide film and thin film formation device |
| US5846888A (en) * | 1996-09-27 | 1998-12-08 | Micron Technology, Inc. | Method for in-situ incorporation of desirable impurities into high pressure oxides |
| JP2000012864A (en) * | 1998-06-22 | 2000-01-14 | Semiconductor Energy Lab Co Ltd | Manufacture of semiconductor device |
| JP2007158371A (en) * | 2007-02-02 | 2007-06-21 | Semiconductor Energy Lab Co Ltd | Method of manufacturing semiconductor device |
| JP2014103175A (en) * | 2012-11-16 | 2014-06-05 | Fuji Electric Co Ltd | Silicon carbide semiconductor device and silicon carbide semiconductor device manufacturing method |
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