JPH0777205B2 - Semiconductor diamond and method for manufacturing the same - Google Patents
Semiconductor diamond and method for manufacturing the sameInfo
- Publication number
- JPH0777205B2 JPH0777205B2 JP62137701A JP13770187A JPH0777205B2 JP H0777205 B2 JPH0777205 B2 JP H0777205B2 JP 62137701 A JP62137701 A JP 62137701A JP 13770187 A JP13770187 A JP 13770187A JP H0777205 B2 JPH0777205 B2 JP H0777205B2
- Authority
- JP
- Japan
- Prior art keywords
- diamond
- semiconductor diamond
- semiconductor
- synthesis method
- present
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
- H10D62/00—Semiconductor bodies, or regions thereof, of devices having potential barriers
- H10D62/80—Semiconductor bodies, or regions thereof, of devices having potential barriers characterised by the materials
- H10D62/83—Semiconductor bodies, or regions thereof, of devices having potential barriers characterised by the materials being Group IV materials, e.g. B-doped Si or undoped Ge
- H10D62/8303—Diamond
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
- H10D62/00—Semiconductor bodies, or regions thereof, of devices having potential barriers
- H10D62/80—Semiconductor bodies, or regions thereof, of devices having potential barriers characterised by the materials
- H10D62/83—Semiconductor bodies, or regions thereof, of devices having potential barriers characterised by the materials being Group IV materials, e.g. B-doped Si or undoped Ge
- H10D62/834—Semiconductor bodies, or regions thereof, of devices having potential barriers characterised by the materials being Group IV materials, e.g. B-doped Si or undoped Ge further characterised by the dopants
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
- Carbon And Carbon Compounds (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は電子機器等に利用される半導体特性を有するダ
イヤモンドに関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to a diamond having semiconductor characteristics, which is used in electronic devices and the like.
ダイヤモンドは、バンドギヤツプが5.5eVであり本来絶
縁性のものであるが、SiやGeなどと同様に不純物をドー
ピングすることにより不純物準位を形成し、Ｐ型及びＮ
型の半導性を持たせることが当然考えられる。Although diamond has a bandgap of 5.5 eV and is essentially insulating, diamond forms an impurity level by doping with an impurity like Si and Ge to form a P-type and an N-type.
It is naturally conceivable to give the mold semiconductivity.
実際、天然ダイヤモンドの中にはＢを含有したＰ型半導
体が存在し、II bダイヤと呼ばれている。このII bダイ
ヤは超高圧合成法によつても製造できる。しかしＮ型の
半導性を示すダイヤモンドは天然には存在しない。ま
た、超高圧合成法で製造されたものでもＮ型の半導性が
確認された例はない。In fact, there is a P-type semiconductor containing B in natural diamond, which is called II b diamond. This IIb diamond can also be manufactured by an ultra-high pressure synthesis method. However, N-type semiconducting diamond does not exist in nature. In addition, there is no example in which the N-type semiconductivity is confirmed even in the one manufactured by the ultrahigh pressure synthesis method.
PN接合を利用した半導体ダイヤモンドデバイスを形成す
るためにはＮ型半導体ダイヤモンドが不可欠である。し
かしながら、これまで超高圧合成法やイオン注入法によ
りダイヤモンドへのドーピングが試られているがＮ型半
導体ダイヤモンドを得られた例ではない。そこでＮ型半
導体ダイヤモンドの実現が待望されている。N-type semiconductor diamond is indispensable for forming a semiconductor diamond device using a PN junction. However, although doping of diamond by an ultrahigh pressure synthesis method or an ion implantation method has been tried so far, it is not an example in which an N-type semiconductor diamond is obtained. Therefore, the realization of N-type semiconductor diamond is highly desired.
本発明はこのような現状に鑑みてなされたもので、Ｎ型
半導体ダイヤモンド及びその製法を提供することを目的
とするものである。The present invention has been made in view of the above circumstances, and an object thereof is to provide an N-type semiconductor diamond and a method for producing the same.
発明者等はダイヤモンドへのドーパント元素として通常
まず考えられるＰやAs等のＶ族元素ではなく、これ等Ｖ
族元素より価電子の多いVI族元素の１つであるSeをドー
パントとして用いることを考えついた。そして、種々実
験研究の結果、例えば気相薄膜合成法、超高圧単結晶合
成法、イオン注入法等によりSeを含有するダイヤモンド
を製造することができ、このSeドープダイヤモンドはSe
の形成したドナーレベルからの自由電子によりＮ型の半
導性を示すことを見出して、本発明に到達したのであ
る。The inventors of the present invention did not consider V group elements such as P and As, which are usually considered as the dopant elements for diamond, to use these V elements.
It was conceived to use Se, which is one of the group VI elements having more valence electrons than the group elements, as a dopant. Then, as a result of various experimental studies, a diamond containing Se can be produced by, for example, a vapor phase thin film synthesis method, an ultrahigh pressure single crystal synthesis method, an ion implantation method, and the like.
The inventors arrived at the present invention by discovering that N-type semiconductivity is exhibited by free electrons from the formed donor level.
すなわち、本発明はドーパント元素としてSeを含有して
なる半導体ダイヤモンドに関するものであり、Seの濃度
が１×1010〜１×1020〔cm-3〕であるものが特に好まし
い。That is, the present invention relates to a semiconductor diamond containing Se as a dopant element, and a Se concentration of 1 × 10 10 to 1 × 10 20 [cm −3 ] is particularly preferable.
さらに本発明はSeを含有してなる半導体ダイヤモンドを
製造する方法として、原料ガス中のSeの原子数とＣの原
子数の比Se/C（％）が0.001〜1.0％である原料ガスを用
いて気相薄膜合成法によりSeを含有してなる半導体ダイ
ヤモンドを得ることを特徴とする半導体ダイヤモンドの
製造方法、超高圧合成法によりドーパント元素としてSe
を含有してなる半導体ダイヤモンドを得ることを特徴と
する半導体ダイヤモンドの製造方法及びイオン注入法に
よりドーパント元素としてSeを含有してなる半導体ダイ
ヤモンドを得ることを特徴とする半導体ダイヤモンドの
製造方法を提供する。Furthermore, the present invention uses a raw material gas having a ratio Se / C (%) of the number of Se atoms and the number of C atoms in the raw material gas of 0.001 to 1.0% as a method for producing a semiconductor diamond containing Se. Method for producing semiconductor diamond, characterized by obtaining Se-containing semiconductor diamond by a vapor phase thin film synthesis method, and Se as a dopant element by an ultra-high pressure synthesis method.
Provided is a method for producing a semiconductor diamond, which comprises obtaining a semiconductor diamond containing Si, and a method for producing a semiconductor diamond comprising obtaining Se as a dopant element by an ion implantation method. .
ダイヤモンドは、IV族元素Ｃの共通結合で構成されてい
る。不純物としてダイヤモンド中に入つたVI元素のSeが
Ｃの格子位置に置換されると、共有結合に携わらない外
殻電子が２個存在することになり、これらはドナー電子
となつてダイヤモンドはＮ型の半導性を示すと考えられ
る。つまりSeはダイヤモンドにドープされて、禁制帯中
にドナーレベルを形成する。Diamond is composed of a common bond of group IV element C. When the VI element Se, which has entered the diamond as an impurity, is substituted at the lattice position of C, there are two outer shell electrons that are not involved in the covalent bond. These are donor electrons, and the diamond is N-type. It is considered to exhibit semiconductivity of. That is, Se is doped in diamond and forms a donor level in the forbidden band.
また、Seが、たとえばＣの格子間に入り、Ｃの空孔とベ
アになつた場合のように、Ｃの格子位置に置換されてい
なくても、ドナーレベルを形成できる場合もあると予想
される。また実際、以上のような考えにもとづき、Seド
ープダイヤモンドを作成したところＮ型の半導性を示す
ことが確認された。Further, it is expected that the donor level can be formed even if the Se is not substituted at the C lattice position, as in the case where Se enters between the C lattices and becomes bare with the C vacancies. It In fact, it was confirmed that when Se-doped diamond was produced based on the above idea, it exhibits N-type semiconductivity.
本発明のSeドープ半導体ダイヤモンドにおいて、Se濃度
は１×1010〜１×1020〔cm-1〕であることが有効であり
好ましい。Seの濃度が１×1010〜１×1020〔cm-1〕未満
では半導体として用いるには抵抗率が高くなりすぎる
し、１×1020〔cm-1〕を越えると電導形態が金属的にな
り半導体としての性質を失なう。In the Se-doped semiconductor diamond of the present invention, it is effective and preferable that the Se concentration is 1 × 10 10 to 1 × 10 20 [cm −1 ]. When the Se concentration is less than 1 × 10 10 to 1 × 10 20 [cm −1 ], the resistivity becomes too high for use as a semiconductor, and when it exceeds 1 × 10 20 [cm −1 ], the conductive form is metallic. And loses its properties as a semiconductor.
本発明のSeドープ半導体ダイヤモンドは気相薄膜合成
法、超高圧単結晶合成法、イオン注入法等の公知技術を
用いて製造することができ、いずれの方法によつても得
られたSeドープ半導体ダイヤモンドの性質に差異はなか
つた。The Se-doped semiconductor diamond of the present invention can be produced by using a known technique such as a vapor phase thin film synthesis method, an ultrahigh pressure single crystal synthesis method, an ion implantation method, etc., and the Se-doped semiconductor diamond obtained by any method There was no difference in the properties of diamond.
気相薄膜合成法により本発明のSeドープ半導体ダイヤモ
ンドを製造する場合、原料ガス中のSe原子数とＣ原子数
の比Se/C比が0.001％〜1.0％として行なうことが好まし
い。この範囲内で行なうことにより得られたダイヤ中の
Se濃度を半導体として有効な１×1010〜１×1020〔c
m-1〕にすることができるからである。When the Se-doped semiconductor diamond of the present invention is manufactured by the vapor phase thin film synthesis method, it is preferable that the ratio Se / C ratio of the number of Se atoms to the number of C atoms in the source gas is 0.001% to 1.0%. In the diamond obtained by performing within this range
Effective Se concentration of 1 × 10 10 to 1 × 10 20 [c
m -1 ].
原材料としては、Ｃ供給源として例えばCH4,C2H6,C3H8
等の炭化水素、CH2OH,C2H5OH等のアルコール等が挙げら
れ、Se供給源としては例えばH2Seが挙げられる。As a raw material, for example, CH 4 , C 2 H 6 , C 3 H 8 as a C supply source
And the like, alcohols such as CH 2 OH and C 2 H 5 OH, and the like, and examples of the Se supply source include H 2 Se.
気相薄膜合成法として種々の従来技術を応用できる。一
例としてマイクロ波プラズマCVD法を用いる場合を説明
すると、チヤンバー内に反応ガスを導入しておき、一方
マグネトロンから発振されたマイクロ波を方形導波管に
よりチヤンバーまで導き、チヤンバー内反応ガスに放電
を起してダイヤモンドの合成反応を行う。Various conventional techniques can be applied as a vapor phase thin film synthesis method. To explain the case of using the microwave plasma CVD method as an example, the reaction gas is introduced into the chamber, while the microwave oscillated from the magnetron is guided to the chamber by the rectangular waveguide, and the reaction gas in the chamber is discharged. Then, the diamond synthesis reaction is performed.
本発明のSeドープ半導体ダイヤモンドを気相薄膜合成
法、超高圧単結晶合成法又はイオン注入法で得る具体的
条件、方法については、以下の実施例にて詳説する。Specific conditions and methods for obtaining the Se-doped semiconductor diamond of the present invention by the vapor phase thin film synthesis method, the ultrahigh pressure single crystal synthesis method or the ion implantation method will be described in detail in the following examples.
実施例１ 公知のマイクロ波プラズマCVD法にて、CH4:0.5％、H2Se
0.000005〜0.005％、残部H2からなる反応ガスを原料と
してダイヤモンド単結晶基板（111）面上に、1.0μｍの
厚さの本発明のSeドープダイヤモンド膜を成長させた。
反応系内圧力は30Torr、マイクロ波は2.45GHz、出力350
Wであつた。Example 1 CH 4 : 0.5%, H 2 Se by a known microwave plasma CVD method
Using a reaction gas composed of 0.000005 to 0.005% and the balance H 2 as a raw material, a Se-doped diamond film of the present invention having a thickness of 1.0 μm was grown on a diamond single crystal substrate (111) surface.
Reaction system pressure is 30 Torr, microwave is 2.45 GHz, output 350
It was W.
得られたSeドープダイヤエピタキシヤル膜の抵抗率測定
とホール測定を行つたところ、ホール係数はいずれも
（−）でありＮ型半導体であることが確認された。When the resistivity measurement and the hole measurement of the obtained Se-doped diamond epitaxial film were performed, it was confirmed that the Hall coefficients were all (-) and that the film was an N-type semiconductor.
さらにSIMSによりダイヤモンド中のSe濃度の測定を行つ
た。Se/C％及び自由電子密度、電子移動度、Se濃度の測
定結果を表１にまとめて示す。なお、No.1の試料のSe濃
度は自由電子密度から推定した値である。Furthermore, the Se concentration in diamond was measured by SIMS. Table 1 collectively shows the measurement results of Se / C%, free electron density, electron mobility, and Se concentration. The Se concentration of the No. 1 sample is a value estimated from the free electron density.
実施例２ 原料のダイヤモンド粉末にSeを混入したものをFe−Ni溶
媒に溶かしこみ5GPa、約1400℃という条件下に７時間置
くことで超高圧法によりSeドープダイヤモンドを合成で
きた。得られたダイヤモンドについて、実施例１と同様
の測定を行つたところ、ホール係数はやはり（−）であ
りＮ型半導体であると確認できた。原料のSe原子数とＣ
原子数の比Se/C（％）、自由電子密度、電子移動度、Se
濃度を表２にまとめて示す。 Example 2 A Se-doped diamond could be synthesized by an ultrahigh pressure method by dissolving a raw material diamond powder mixed with Se and dissolving it in a Fe-Ni solvent and keeping it at 5 GPa and about 1400 ° C. for 7 hours. When the obtained diamond was measured in the same manner as in Example 1, the Hall coefficient was (−) and it was confirmed that the diamond was an N-type semiconductor. Raw material Se atom number and C
Atomic ratio Se / C (%), free electron density, electron mobility, Se
The concentrations are summarized in Table 2.
実施例３ イオン注入により、Se加速電圧180keV、Se注入量４×10
151/cm2の条件で、ダイヤモンド単結晶にSeを注入し
て、本発明のSeドープダイヤモンドを製造した。得られ
たSeドープダイヤモンドに真空中でアニールを施した
後、ホール測定と抵抗率測定を行つた。ホール係数は
（−）でありＮ型半導体であることが確認された。Se注
入部の平均自由電子密度は1015〔1/cm3〕、電子移動度
は10〔cm2/V.s〕であつた。 Example 3 By ion implantation, Se acceleration voltage 180 keV, Se implantation amount 4 × 10
In 15 1 / cm 2 conditions, by injecting Se diamond single crystal, to produce a Se-doped diamond of the present invention. After the obtained Se-doped diamond was annealed in vacuum, hole measurement and resistivity measurement were performed. The Hall coefficient was (-), and it was confirmed to be an N-type semiconductor. The average free electron density of the Se injection part was 10 15 [1 / cm 3 ] and the electron mobility was 10 [cm 2 / Vs].
以上の説明と実施例の結果から明らかなように、本発明
のSeを含有したダイヤモンドは、従来得られていなかつ
たＮ型の半導体ダイヤモンドを実現したものである。し
たがつて本発明のSeを含有するダイヤモンドを用いるこ
とにより、PN接合を利用したダイヤモンド半導体デバイ
スの作製が可能となる。As is clear from the above description and the results of the examples, the Se-containing diamond of the present invention realizes an N-type semiconductor diamond which has never been obtained. Therefore, the use of the Se-containing diamond of the present invention makes it possible to manufacture a diamond semiconductor device utilizing a PN junction.
また、サーミスターへの応用や、単に導電性の要求され
るダイヤモンドコーテイング膜としての応用も考えられ
る。これらの場合には多結晶ダイヤモンドでも有効であ
る。Further, application to a thermistor or application as a diamond coating film which is simply required to have conductivity can be considered. In these cases, polycrystalline diamond is also effective.
このようにダイヤモンド半導体としての広い用途への可
能性を開く本発明のSeドープダイヤモンドは、その製法
上は公知技術を応用することで容易に得られる点でも有
利である。As described above, the Se-doped diamond of the present invention, which opens up a wide range of applications as a diamond semiconductor, is advantageous in that it can be easily obtained by applying a known technique in terms of its production method.
Claims (5)
導体ダイヤモンド。1. A semiconductor diamond containing Se as a do band element.
1020〔cm-3〕の濃度で含有する特許請求の範囲第１項に
記載される半導体ダイヤモンド。2. Se of 1 × 10 10 to 1 × as a do band element
The semiconductor diamond according to claim 1, which is contained at a concentration of 10 20 [cm -3 ].
Se/C（％）が0.001〜1.0％である原料ガスを用いて気相
薄膜合成法により、ドーパント元素としてSeを含有して
なる半導体ダイヤモンドを得ることを特徴とする半導体
ダイヤモンドの製造方法。3. The ratio of the number of Se atoms and the number of C atoms in the source gas.
A method for producing a semiconductor diamond, characterized in that a semiconductor diamond containing Se as a dopant element is obtained by a vapor phase thin film synthesis method using a source gas having a Se / C (%) of 0.001 to 1.0%.
Seを含有してなる半導体ダイヤモンドを得ることを特徴
とする半導体ダイヤモンドの製造方法。4. As a dopant element by ultra-high pressure synthesis method
A method for producing a semiconductor diamond, which comprises obtaining a semiconductor diamond containing Se.
Seを含有してなる半導体ダイヤモンドを得ることを特徴
とする半導体ダイヤモンドの製造方法。5. As a dopant element by an ion implantation method
A method for producing a semiconductor diamond, which comprises obtaining a semiconductor diamond containing Se.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62137701A JPH0777205B2 (en) | 1987-06-02 | 1987-06-02 | Semiconductor diamond and method for manufacturing the same |
| DE3818719A DE3818719C2 (en) | 1987-06-02 | 1988-06-01 | N-type semiconductor diamond and process for producing the same |
| US07/201,151 US5001452A (en) | 1987-06-02 | 1988-06-02 | Semiconducting diamond and process for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62137701A JPH0777205B2 (en) | 1987-06-02 | 1987-06-02 | Semiconductor diamond and method for manufacturing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63302517A JPS63302517A (en) | 1988-12-09 |
| JPH0777205B2 true JPH0777205B2 (en) | 1995-08-16 |
Family
ID=15204795
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62137701A Expired - Fee Related JPH0777205B2 (en) | 1987-06-02 | 1987-06-02 | Semiconductor diamond and method for manufacturing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0777205B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5324609B2 (en) * | 2011-03-22 | 2013-10-23 | 日本電信電話株式会社 | Diamond semiconductor and manufacturing method |
| JP6264773B2 (en) * | 2013-08-05 | 2018-01-24 | 住友電気工業株式会社 | Tool comprising nano-polycrystalline diamond, machining system, and machining method |
-
1987
- 1987-06-02 JP JP62137701A patent/JPH0777205B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63302517A (en) | 1988-12-09 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |