JP2645586B2 - Germanium thin film n-type conductor and method of manufacturing the same - Google Patents
Germanium thin film n-type conductor and method of manufacturing the sameInfo
- Publication number
- JP2645586B2 JP2645586B2 JP1077755A JP7775589A JP2645586B2 JP 2645586 B2 JP2645586 B2 JP 2645586B2 JP 1077755 A JP1077755 A JP 1077755A JP 7775589 A JP7775589 A JP 7775589A JP 2645586 B2 JP2645586 B2 JP 2645586B2
- Authority
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- Japan
- Prior art keywords
- thin film
- temperature
- germanium thin
- germanium
- sample
- 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.)
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Links
- 239000010409 thin film Substances 0.000 title claims description 42
- 229910052732 germanium Inorganic materials 0.000 title claims description 31
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 title claims description 31
- 239000004020 conductor Substances 0.000 title claims description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 238000000137 annealing Methods 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 20
- 229910021478 group 5 element Inorganic materials 0.000 claims description 3
- 230000001747 exhibiting effect Effects 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 claims 1
- 238000000034 method Methods 0.000 description 16
- 239000010408 film Substances 0.000 description 12
- 238000005259 measurement Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 238000010586 diagram Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 239000011521 glass Substances 0.000 description 7
- 238000005229 chemical vapour deposition Methods 0.000 description 5
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 238000004377 microelectronic Methods 0.000 description 4
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 229910008310 Si—Ge Inorganic materials 0.000 description 2
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229910021424 microcrystalline silicon Inorganic materials 0.000 description 2
- 230000005676 thermoelectric effect Effects 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000005678 Seebeck effect Effects 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910000078 germane Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910000623 nickel–chromium alloy Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Pressure Sensors (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ この発明は、電子回路に使用するための導電体に係
り、マイクロエレクトロニクス範囲に属する。この導電
体はプラズマCVD等で比較的低温で堆積した半導体材料
をアニール処理することにより得られた半導体材料で成
るにも拘らず、比較的大きな導電率をもち、しかもその
温度係数が金属並みに小さく、他方では熱電能（ゼーベ
ック係数の大きさ）が半導体のように大きいという特徴
を備えていることが発見されてから、微細な熱電効果素
子を構成することができ、電力測定用のパワーセンサの
構成素材とすることができる。Description: TECHNICAL FIELD The present invention relates to a conductor for use in electronic circuits, and belongs to the microelectronics field. This conductor has a relatively large conductivity, and its temperature coefficient is comparable to that of metal, despite being composed of a semiconductor material obtained by annealing a semiconductor material deposited at a relatively low temperature by plasma CVD or the like. Since it was discovered that the thermoelectric effect (the magnitude of the Seebeck coefficient) on the other hand was as large as that of a semiconductor, it was possible to construct a fine thermoelectric element, and a power sensor for power measurement Constituent material.
また、この導電体は機械的ひずみ（あるいは応力）に
よってその抵抗が変化するエラスト抵抗効果（あるいは
ピエゾ抵抗効果）を備えているから、ひずみあるいは力
のセンサの構成素材とすることができる。すなわち、各
種のセンサ，エレクトロニクス用素材を提供するもので
ある。Further, since this conductor has an elast resistance effect (or piezo resistance effect) in which the resistance changes due to mechanical strain (or stress), it can be used as a constituent material of a strain or force sensor. That is, various sensors and materials for electronics are provided.
［従来の技術］ センサ，エレクトロニクス用素材として、各種の金
属，合金，単元素半導体，化合物半導体，半金属，アモ
ルファス材料などが数多く知られているところである。
従来のこの種の素材の特性を見ると、いずれも一方で特
長があると、他方で欠点があるという具合であった。た
とえば、単元素半導体であるｐ形シリコンのピエゾ抵抗
効果は合金のニッケルクロムの102倍も大きいが、抵抗
の温度係数が103倍も大きいという具合であった。ゼー
ベック係数と導電率あるいはその温度係数についても同
様であったが、最近では、同一出願人により提案された
「シリコン・ゲルマニウム液晶薄膜導電体」（特願昭60
−186900号）において、一部実現されている。例えば、
暗導電率と、ゼーベック係数との関係を示す第１図に示
されているように、微結晶化シリコン・ゲルマニウム
（以下、μｃ−Si−Geと記す）薄膜においては、暗導電
率が100S・cm-1以上で、かつ、ゼーベック係数として10
0μV/K以上が得られている。しかもその暗導電率の温度
係数としては１％/K以下となっている。しかしながら、
ｎ形膜においては、暗導電率はμｃ−Si−Geの場合でも
高々20S・cm-1である。また、ゲルマニウム蒸着膜につ
いても検討されているが、結晶欠陥等が発生し易いた
め、暗導電率の大きな膜を得るのは困難であった（例え
ば、小沼義治；「Ge蒸着膜の熱電特性」,J.Inst.Elect.
Eng.Japan.,7/'69,pp.1406〜1412に記載されている）。[Prior Art] Many materials, such as various metals, alloys, single element semiconductors, compound semiconductors, semimetals and amorphous materials, are known as materials for sensors and electronics.
Looking at the characteristics of this type of conventional material, it was found that all had characteristics on one side and had disadvantages on the other. For example, the piezoresistive effect of p-type silicon of a single element semiconductor is greater 10 double nickel chromium alloy, the temperature coefficient of resistance was so on greater 10 3 times. The same was true for the Seebeck coefficient and the electrical conductivity or its temperature coefficient. Recently, however, a “silicon-germanium liquid crystal thin film conductor” proposed by the same applicant (Japanese Patent Application No.
No. 186900). For example,
As shown in FIG. 1 showing the relationship between the dark conductivity and the Seebeck coefficient, in a microcrystalline silicon-germanium (hereinafter referred to as μc-Si-Ge) thin film, the dark conductivity is 100 S · cm -1 or more, and 10 as Seebeck coefficient
0 μV / K or more is obtained. Moreover, the temperature coefficient of the dark conductivity is 1% / K or less. However,
In the n-type film, the dark conductivity is at most 20 S · cm −1 even in the case of μc-Si-Ge. In addition, germanium vapor-deposited films have been studied, but it is difficult to obtain a film having a large dark conductivity because crystal defects and the like are easily generated (for example, Yoshiharu Konuma; "Thermoelectric properties of Ge vapor-deposited films") , J.Inst.Elect.
Eng. Japan., 7 / '69, pp. 1406-1412).
すなわち、センサ用の薄膜ｎ型導電体の材質として、
ゲルマニウムを用いることは広く知られているが（特開
昭47−23083号公報 応力変換素子の製造方法）、その
素子は比抵抗５×10-2Ω cm程度に過ぎず、暗導電率を
大きくすることができなかった。That is, as the material of the thin film n-type conductor for the sensor,
It is widely known that germanium is used (Japanese Patent Application Laid-Open No. 47-23083, a method for manufacturing a stress conversion element), but the element has a specific resistance of only about 5 × 10 −2 Ωcm and a large dark conductivity. I couldn't.
［発明が解決しようとする問題点］ 半導体の特長であるセンサ，エレクトロニクスに利用
したい優れた特性と、低抵抗（高導電率）およびその温
度係数が小さいという金属的性質をともに備え、ガラス
基板はじめあらゆる絶縁性基板上に堆積でき、しかも加
工がし易いという生産技術上の要請をすべて備えたマイ
クロエレクトロニクス用導電体を実現すること、特にｎ
形導電体（以下の説明ではｎ形を略記することもある）
を実現することがこの発明としての課題である。[Problems to be Solved by the Invention] Both the excellent characteristics of semiconductors, which are desirable for use in sensors and electronics, and the metallic properties of low resistance (high conductivity) and a low temperature coefficient, are suitable for glass substrates. To realize a conductor for microelectronics that can be deposited on any insulating substrate and that has all the requirements of production technology that it is easy to process, especially n
Shaped conductor (n-type may be abbreviated in the following description)
Is an object of the present invention.
［問題点を解決するための手段］ この発明では、薄膜導電体として、プラズマCVD法を
用いて低温堆積した薄膜を熱アニール処理して得られた
微結晶化ゲルマニウム薄膜が、従来技術の所産に比較し
て、特に高い導電率をもち、その温度係数が小さく、し
かも、大きなゼーベック効果とエラスト抵抗（ピエゾ抵
抗）効果を示すという発明者により発見された事実に基
く。特に、リン（Ｐ）など第Ｖ族元素を含むゲルマニウ
ム（Ge）のアモルファス相の薄膜を熱処理したときに見
られる。抵抗の変化特性を利用する。すなわち、絶縁性
をもつ基板上に、ゲルマニウム薄膜をマイクロエレクト
ロニクスの技法（たとえばプラズマCVD法，光CVD法な
ど）で作成した後、上記の変化特性に着目しながら熱ア
ニール処理を施し、更に、その薄膜の両端に一対の電極
を備えて、電流の入・出力端子として、上記素材の電流
現象（輸送現象）をセンサに利用できる構造とする。[Means for Solving the Problems] In the present invention, a microcrystalline germanium thin film obtained by subjecting a thin film deposited at a low temperature by a plasma CVD method to a thermal annealing treatment as a thin film conductor is a product of the prior art. In comparison, it is based on the fact discovered by the inventor that it has a particularly high conductivity, has a low temperature coefficient, and exhibits a large Seebeck effect and an elast resistance (piezo resistance) effect. In particular, it is observed when a thin film of an amorphous phase of germanium (Ge) containing a group V element such as phosphorus (P) is heat-treated. The change characteristics of resistance are used. That is, after a germanium thin film is formed on a substrate having an insulating property by a microelectronic technique (for example, a plasma CVD method, a photo CVD method, etc.), a thermal annealing process is performed while paying attention to the above change characteristics, and A structure is provided in which a pair of electrodes is provided at both ends of the thin film, and current phenomena (transport phenomena) of the above-mentioned material can be used as a sensor as current input / output terminals.
［作用］ こうして作られたゲルマニウム薄膜ｎ形導電体の導電
率は、少なくとも30S・cm-1以上であり、導電率の温度
係数は0.5％/K以下である。しかも、熱電能（ゼーベッ
ク係数）の大きさは少なくとも絶対値100μV/K（ｎ形で
は、熱電能の極性は負となる）を有し、エラスト抵抗効
果（ピエゾ抵抗効果）の大きさを示すゲージ率（抵抗変
化率／ひずみ）は少なくとも絶対値10（ｎ形では、両す
みの極性は負となる）を備えている。[Action] The conductivity of the n-type germanium thin film conductor thus formed is at least 30 S · cm −1 or more, and the temperature coefficient of the conductivity is 0.5% / K or less. Moreover, the magnitude of the thermoelectric power (Seebeck coefficient) has at least an absolute value of 100 μV / K (in the case of n-type, the polarity of the thermoelectric power becomes negative) and indicates the magnitude of the elast resistance effect (piezoresistance effect). The rate (rate of resistance change / strain) has at least an absolute value of 10 (in the n-type, the polarity of both corners is negative).
［実施例］ この発明の薄膜ｎ形導電体のマイクロエレクトロニク
スの技法の一つであるCVD（Chemical Vapour Depositio
n）法および熱アニール法を組み合わせた方法で製造す
る方法について述べる。[Embodiment] CVD (Chemical Vapor Depositio) which is one of the techniques of microelectronics of the thin film n-type conductor of the present invention.
A method of manufacturing by combining the n) method and the thermal annealing method will be described.
先ず、CVD法について述べる。CVDには、市販のプラズ
マCVD炉で差支えないし、製造装置は要するにアモルフ
ァス相を形成できるものであればよい。ここで説明する
実施例では、ｎ形の導電体を形成するものとする。First, the CVD method will be described. A commercially available plasma CVD furnace may be used for the CVD, and the manufacturing apparatus may be any as long as it can form an amorphous phase. In the embodiment described here, an n-type conductor is formed.
炉内に導入する原料ガスとしては水素希釈のゲルマン
（GeH4）を用いる。ｎ形ドーパントとして水素希釈のフ
ォスフィン（PH3）を添加する。堆積条件の一例を第１
表に示す。基板には少なくとも表面が絶縁性をもつ基
板、例えばガラス基板、マイカポリミイドフィルムはじ
め各種半導体基板もしくは表面が絶縁材で覆われた金属
板が用いられる。Hydrogen-diluted germane (GeH 4 ) is used as a source gas introduced into the furnace. Phosphine (PH 3 ) diluted with hydrogen is added as an n-type dopant. Example of deposition conditions
It is shown in the table. As the substrate, a substrate having at least a surface having an insulating property, for example, a glass substrate, a mica-polyimide film or various semiconductor substrates or a metal plate whose surface is covered with an insulating material is used.
次に熱アニールの方法について述べる。 Next, a method of thermal annealing will be described.
熱アニールには第２図に示すように市販の赤外線（I
R）加熱炉を用いた。CVD法を用いて堆積した微結晶化ゲ
ルマニウム膜が堆積してある試料はIR炉内のサンプルホ
ルダー（図示せず）内に配列される。As shown in FIG. 2, a commercially available infrared ray (I
R) A heating furnace was used. The sample on which the microcrystalline germanium film deposited using the CVD method is deposited is arranged in a sample holder (not shown) in the IR furnace.
このとき、該試料の両端部には、抵抗率がモニターで
きるよう薄膜電極，例えばクロム／白金多層膜を真空蒸
着法等を用いて設ける。この試料は、IR炉で所定の昇温
レートで加熱・昇温され、設定アニール温度で短時間保
持され、すぐに降温される。このとき、試料の抵抗率お
よび温度は、第２図に示すようにリード線10と抵抗計11
および熱電対12と電圧計13とを通して各々随時計測さ
れ、各々計測されたデータは逐時パソコン14に転送さ
れ、パソコン14画面上で観測できるという特徴をもって
いる。試料の昇温レート，設定アニール温度，降温レー
ト等は、熱電対15およびIR炉温度コントローラー16によ
り制御される。At this time, a thin film electrode, for example, a chromium / platinum multilayer film is provided on both ends of the sample by a vacuum deposition method or the like so that the resistivity can be monitored. This sample is heated and heated at a predetermined heating rate in an IR furnace, kept for a short time at the set annealing temperature, and immediately cooled. At this time, the resistivity and the temperature of the sample are measured by the lead wire 10 and the resistance meter 11 as shown in FIG.
In addition, it is measured at any time through the thermocouple 12 and the voltmeter 13, and the measured data is sequentially transferred to the personal computer 14 and can be observed on the screen of the personal computer 14. The temperature rise rate, set annealing temperature, temperature fall rate, and the like of the sample are controlled by a thermocouple 15 and an IR furnace temperature controller 16.
第３図は熱アニール時における試料温度と試料の抵抗
率との関係の一例を示す図で、横軸は試料温度（℃）
を、また、縦軸は抵抗率（Ω・cm）を示す。この第３図
は現象を袴張して模式的に示すものであるが、試料の温
度変化に対する抵抗率の変化する割合、すなわち活性化
エネルギーの値は各キンク点ａ〜ｅを境にして異なる。
第４図は各キンク点まで昇温し、すぐに降温させた場合
の、抵抗率の変化する模様を示す図である。キンク点ａ
まで昇温し降温させた場合を矢印，′で示す。この
とき、熱アニール前後での室温における抵抗率の変化は
見られなかった。同様に各キンク点ｂ〜ｅまでそれぞれ
昇温し降温させた場合の各抵抗率の変化する模様を矢印
，′，，′，，′，，′で示す。第４
図に示されているように、室温での抵抗率は、キンク点
が高くなる程小さくなる結果が得られた。第３図および
第４図から判断すると、キンク点ａまでは常温における
抵抗値がもとの状態に戻ることができる再帰可能領域で
あり、キンク点ａ〜ｅ間は再帰しない領域といえる。ま
た、ｅ点を超えた温度では膜に異なる変質（破壊）が生
じていることが知れる。ａ〜ｅ間の領域ではｂ〜ｃ〜ｄ
の範囲でアモルファス相に変化が生じ、安定した良い特
性のｎ形導電体が形成されていると認められる。FIG. 3 is a diagram showing an example of the relationship between the sample temperature and the resistivity of the sample during thermal annealing, wherein the horizontal axis is the sample temperature (° C.).
The vertical axis indicates the resistivity (Ω · cm). FIG. 3 schematically shows the phenomenon, but the rate of change of the resistivity with respect to the temperature change of the sample, that is, the value of the activation energy is different at each of the kink points a to e. .
FIG. 4 is a diagram showing a pattern in which the resistivity changes when the temperature is raised to each kink point and immediately lowered. Kink point a
The case where the temperature is increased and decreased is indicated by an arrow and ′. At this time, there was no change in resistivity at room temperature before and after thermal annealing. Similarly, a pattern in which each resistivity changes when the temperature is raised and lowered to each of the kink points b to e is indicated by arrows, ',,', ',', '. 4th
As shown in the figure, the result that the resistivity at room temperature becomes smaller as the kink point becomes higher. Judging from FIGS. 3 and 4, it can be said that the region up to the kink point a is a recursive region where the resistance value at normal temperature can return to the original state, and the region between the kink points a to e does not recur. It is also known that a different quality (destruction) occurs in the film at a temperature exceeding the point e. b to c to d in the region between a to e
It is recognized that a change occurs in the amorphous phase in the range described above, and that an n-type conductor having stable and good characteristics is formed.
第５図は、前記第１表の条件でガラス基板上に堆積し
たゲルマニウム薄膜と、続けて熱アニールを施した微結
晶化ゲルマニウム膜とのレーザラマンスペクトルの一例
を示す図である。測定法としては直角散乱法を用いた。
図中、横軸はラマンシフト（cm-1）を、縦軸はラマン強
度（任意単位）をそれぞれ示している。波形ＡはCVD法
で堆積した膜およびキンク点a,bまで昇温させた場合で
スペクトルの半値幅が大きいので、微結晶相中に可成り
のアモルファス相が含まれている。波形Ｂは、熱アニー
ルをキンク点ｃまで施した膜で、波形Ａとほぼ同一形状
のスペクトルが得られたが、300cm-1付近のスペクトル
のピーク値が増大し、かつ半値幅が小さくなった。ま
た、波形Ｃは熱アニールを各キンク点d,eまでそれぞれ
施した膜で、ほぼ同一形状のスペクトルが得られ300cm
-1付近のスペクトルのピーク値は急激に増大し、かつス
ペクトル値が狭くなり、大部分が微結晶相から構成され
ている。このように、一定温度以上の熱アニールを施す
ことにより微結晶化の割合を増大させ、かつ抵抗率を小
さく制御できることが確認された。なお、抵抗率の減少
に伴い、300cm-1付近のレーザスペクトルの半値幅は狭
く、かつピーク値が増大している。従って、レーザスペ
クトルの300cm-1付近のピーク値と半値幅を測定するこ
とにより、抵抗率を非破壊で、すなわち、試料に損傷を
与えることなく求めることができる。第６図は、第１表
の条件でガラス基板上に堆積した微結晶化ゲルマニウム
薄膜および熱アニールを施したゲルマニウム薄膜の、暗
導電率およびゼーベック係数の測定に用いたサンプル形
状を示す図で、１はガラス基板、２は微結晶化ゲルマニ
ウム薄膜、３白金薄膜、４はゼーベック係数測定用サン
プルをそれぞれ示す。測定に用いた微結晶化ゲルマニウ
ム薄膜の膜厚は約１μｍである。また、Ｔ＋ΔＴは温接
点を、Ｔは冷接点を示す。パターン形成は通常のホトリ
ソグラフィ技術を用いて、また、白金薄膜形成は真空蒸
着法を用いた。FIG. 5 is a diagram showing an example of a laser Raman spectrum of a germanium thin film deposited on a glass substrate under the conditions shown in Table 1 and a microcrystalline germanium film subsequently subjected to thermal annealing. The orthogonal scattering method was used as the measuring method.
In the figure, the horizontal axis indicates Raman shift (cm -1 ), and the vertical axis indicates Raman intensity (arbitrary unit). Waveform A has a large half-value width of the spectrum when the temperature is raised to the film deposited by the CVD method and the kink points a and b, so that the microcrystalline phase contains a considerable amorphous phase. Waveform B is a film subjected to thermal annealing up to the kink point c, and a spectrum having almost the same shape as that of the waveform A was obtained. However, the peak value of the spectrum near 300 cm -1 was increased and the half width was reduced. . Waveform C is a film subjected to thermal annealing up to each of the kink points d and e.
The peak value of the spectrum near -1 sharply increases and the spectrum value narrows, and most of the spectrum is composed of a microcrystalline phase. As described above, it was confirmed that by performing the thermal annealing at a certain temperature or higher, the rate of microcrystallization can be increased and the resistivity can be controlled to be small. As the resistivity decreases, the half width of the laser spectrum near 300 cm −1 is narrow and the peak value is increasing. Therefore, by measuring the peak value and the half-width around 300 cm -1 of the laser spectrum, the resistivity can be determined nondestructively, that is, without damaging the sample. FIG. 6 is a diagram showing sample shapes used for measurement of dark conductivity and Seebeck coefficient of a microcrystalline germanium thin film and a thermally annealed germanium thin film deposited on a glass substrate under the conditions shown in Table 1. Reference numeral 1 denotes a glass substrate, 2 denotes a microcrystalline germanium thin film, 3 platinum thin film, and 4 denotes a sample for Seebeck coefficient measurement. The thickness of the microcrystalline germanium thin film used for the measurement is about 1 μm. T + ΔT indicates a hot junction, and T indicates a cold junction. The pattern was formed by a usual photolithography technique, and the platinum thin film was formed by a vacuum deposition method.
第７図は、第６図に示したゼーベック係数測定用サン
プル４を用いて得られた熱アニールをキンク点ｅまで施
したゲルマニウム薄膜の暗導電率の温度特性の一例を示
す図である。図中、横軸は、温度を、縦軸は、暗導電率
（σＤ）をそれぞれ示している。図に示すように、温度
による変化が0.5％/K以下と非常に小さい結果が得られ
た。このように暗導電率が温度変化による影響を受けに
くいことは、ICチップ上等に微小な抵抗体等を形成する
上で極めて有利である。FIG. 7 is a diagram showing an example of a temperature characteristic of dark conductivity of a germanium thin film subjected to thermal annealing up to the kink point e obtained by using the Seebeck coefficient measurement sample 4 shown in FIG. In the figure, the horizontal axis represents temperature, and the vertical axis represents dark conductivity (σ D ). As shown in the figure, a very small result was obtained in which the change with temperature was 0.5% / K or less. The fact that the dark conductivity is hardly affected by a change in temperature as described above is extremely advantageous in forming a minute resistor or the like on an IC chip or the like.
第１図は、第６図に示したゼーベック係数測定用サン
プル４を用いて測定した微結晶化ゲルマニウム薄膜（μ
ｃ−Ge）および熱アニールを施したゲルマニウム薄膜の
暗導電率−ゼーベック係数特性を示す図で、横軸に暗導
電率σＤ（Ｓ・cm-1）の大きさを、縦軸にゼーベック係
数α（μV/K）の大きさを示す。図中、三角印は、本発
明による微結晶化ゲルマニウム薄膜および熱アニールを
施したゲルマニウム薄膜の暗導電率およびゼーベック係
数の大きさを表わすものである。熱アニールを施すこと
により、暗導電率を１桁向上できた。また、ゼーベック
係数の大きさとしては絶対値で300μV/K以上のものが得
られている。このゼーベック係数の大きさは、従来のｐ
形膜の２倍近い値であり、熱電効果型センサを構成する
上で極めて有利である。なお、参考のため、従来のｐ形
アモルファスシリコン・ゲルマニウム薄膜（μｃ−Si:G
e）のゼーベック係数の大きさを白丸印で、また、ｐ形
アモルファスシリコン薄膜（μｃ−Si）のゼーベック係
数を黒丸印でそれぞれ示した（特願昭57−051807号で開
示したデータである）。FIG. 1 shows a microcrystalline germanium thin film (μ) measured using the Seebeck coefficient measurement sample 4 shown in FIG.
FIG. 5 is a graph showing dark conductivity-Seebeck coefficient characteristics of a c-Ge) and a thermally annealed germanium thin film, where the horizontal axis represents the magnitude of dark conductivity σ D (S · cm −1 ), and the vertical axis represents the Seebeck coefficient. Indicates the magnitude of α (μV / K). In the figure, triangles indicate the magnitude of the dark conductivity and the Seebeck coefficient of the microcrystalline germanium thin film according to the present invention and the thermally annealed germanium thin film. By performing the thermal annealing, the dark conductivity could be improved by one digit. The magnitude of the Seebeck coefficient is 300 μV / K or more in absolute value. The magnitude of this Seebeck coefficient is
This value is almost twice as large as that of the shape film, and is extremely advantageous in forming a thermoelectric effect type sensor. For reference, a conventional p-type amorphous silicon-germanium thin film (μc-Si: G
The magnitude of the Seebeck coefficient of e) is indicated by a white circle, and the Seebeck coefficient of the p-type amorphous silicon thin film (μc-Si) is indicated by a black circle (data disclosed in Japanese Patent Application No. 57-051807). .
また、第８図に示す歪みゲージ測定用サンプル９を形
成し、ゲージ率を測定した結果、絶対値10以上のもの
（ｎ形の場合、ゲージ率の極性は負となる）が得られて
いる。なお、図中、５はガラス基板、６は熱アニールを
施したゲルマニウム薄膜、7,7′はオーミック電極、8,
8′はAuリボン線をそれぞれ示す。オーミック電極材料
としてはクロム・白金多層薄膜を用いている。また、矢
印はひずみゲージ測定のため、外部より加えた応力の方
向を示している。The strain gauge measurement sample 9 shown in FIG. 8 was formed, and the gage factor was measured. As a result, a sample having an absolute value of 10 or more (in the case of n-type, the polarity of the gage factor was negative) was obtained. . In the figure, 5 is a glass substrate, 6 is a thermally annealed germanium thin film, 7, 7 'are ohmic electrodes, 8,
8 'indicates Au ribbon lines, respectively. A chromium / platinum multilayer thin film is used as the ohmic electrode material. Arrows indicate the directions of externally applied stress for strain gauge measurement.
以上で述べた微結晶化ゲルマニウム薄膜のプラズマCV
D法による堆積条件は、放電圧力、放電パワー、基板温
度に依存することが確認されており、第１表に示した以
外でも形成でき、次に示すような範囲内で、例えば放電
圧力0.5〜10（Torr）、放電パワー密度0.1〜10W/cm2、
基板温度300〜500℃で形成できる。また、光CVD法にお
いては、低温形成、例えば基板温度が200℃前後でも形
成できる。Plasma CV of microcrystalline germanium thin film described above
It has been confirmed that the deposition conditions according to the D method depend on the discharge pressure, discharge power, and substrate temperature. The deposition conditions can be formed in a manner other than those shown in Table 1. 10 (Torr), discharge power density 0.1-10W / cm 2 ,
It can be formed at a substrate temperature of 300 to 500 ° C. Further, in the photo-CVD method, it can be formed at a low temperature, for example, even when the substrate temperature is around 200 ° C.
［効果］ 以上、詳説したように、本発明による微結晶ゲルマニ
ウム薄膜ｎ形導電体は、ＰのようなＶ族元素を含むアモ
ルファス相のゲルマニウム薄膜に、注意深く熱処理を施
して作成したものであり、ゲルマニウムよりなるアモル
ファス相と微結晶相とを混在させることにしたから、次
に示すような固有の効果を有する。[Effects] As described in detail above, the n-type microcrystalline germanium thin film according to the present invention is formed by carefully performing a heat treatment on an amorphous phase germanium thin film containing a group V element such as P; Since the amorphous phase and the microcrystalline phase made of germanium are mixed, the following specific effects are obtained.
（１）暗導電率が30S・cm-1以上と大きな値が得られる
ので小形な抵抗体を絶縁基板上に形成できる。(1) Since a large value of dark conductivity of 30 S · cm −1 or more is obtained, a small resistor can be formed on an insulating substrate.
（２）暗導電率が100S・cm-1以上でゼーベック係数が30
0〜350μV/K以上あるので、高性能な熱電対，高周波パ
ワーセンサ，赤外線センサ，温度センサ等を構成するこ
とができる。(2) Seebeck coefficient of 30 with dark conductivity of 100 S · cm -1 or more
Since it is 0 to 350 μV / K or more, a high-performance thermocouple, high-frequency power sensor, infrared sensor, temperature sensor, and the like can be configured.
（３）暗導電率が100S・cm-1以上と大きいのにかかわら
ず、ゲージ率が絶対値10以上と大きいので、高性能な歪
みセンサ，圧力センサ，ロードセル，タッチセンサを構
成できる。(3) Regardless of the dark conductivity as large as 100 S · cm −1 or more, since the gage factor is as large as 10 or more in absolute value, high-performance strain sensors, pressure sensors, load cells, and touch sensors can be configured.
（４）暗導電率の温度係数が0.5％/K以下と非常に小さ
いので、温度補償を必要としない抵抗体はじめ高周波パ
ワーセンサ，赤外線センサ，歪みセンサ，圧力センサ，
ロードセル等を構成できる。(4) Since the temperature coefficient of dark conductivity is very small, 0.5% / K or less, resistors that do not require temperature compensation, high-frequency power sensors, infrared sensors, strain sensors, pressure sensors,
A load cell or the like can be configured.
（５）プラズマCVD法等比較的簡単な方法と熱アニール
で形成でき、かつ、暗導電率等を容易に制御でき、か
つ、ICプロセスと両立するので、従来のICの中に、温度
センサ，歪みセンサ，圧力センサ等を容易に組み込むこ
とができるので高機能ICを構成できる。また、温度セン
サ，歪みセンサ等を組み合わせた三次元センサを容易
に、かつ、安価に構成できる。(5) Since it can be formed by a relatively simple method such as a plasma CVD method and thermal annealing, and can easily control dark conductivity and the like and is compatible with an IC process, a temperature sensor, Since a strain sensor, a pressure sensor, and the like can be easily incorporated, a high-performance IC can be configured. Also, a three-dimensional sensor combining a temperature sensor, a strain sensor, and the like can be easily and inexpensively configured.
（６）薄膜形成技術により、いろいろな絶縁性基板上
に、広い面積で自由な平面形状にわたり導電体を形成で
きる。(6) Conductors can be formed over various insulating substrates over a wide area and in a free planar shape by a thin film forming technique.
第１図は暗導電率−ゼーベック係数特性を示す図、第２
図は熱アニール制御システムを示す図、第３図は熱アニ
ール処理時の抵抗変化曲線を示す図、第４図は熱アニー
ル温度と抵抗変化特性を示す図、第５図はレーザラマン
スペクトルを示す図、第６図はゼーベック係数測定用サ
ンプル４を示す図、第７図は暗導電率の温度特性を示す
図、第８図は歪みゲージ測定用サンプル９を示す図であ
る。 図中、1,5はガラス基板、２は微結晶化ゲルマニウム薄
膜、３は白金電極、４はゼーベック係数測定用サンプ
ル、６はゲルマニウム薄膜、7,7′はオーミック電極、
8,8′はAuリボン線、９は歪みゲージ測定用サンプルを
それぞれ示す。FIG. 1 is a diagram showing dark conductivity-Seebeck coefficient characteristics, FIG.
FIG. 3 shows a thermal annealing control system, FIG. 3 shows a resistance change curve during thermal annealing, FIG. 4 shows thermal annealing temperature and resistance change characteristics, and FIG. 5 shows a laser Raman spectrum. FIG. 6 is a diagram showing a sample 4 for Seebeck coefficient measurement, FIG. 7 is a diagram showing temperature characteristics of dark conductivity, and FIG. 8 is a diagram showing a sample 9 for strain gauge measurement. In the figure, 1, 5 is a glass substrate, 2 is a microcrystallized germanium thin film, 3 is a platinum electrode, 4 is a sample for Seebeck coefficient measurement, 6 is a germanium thin film, 7, 7 'is an ohmic electrode,
8, 8 'indicate an Au ribbon wire, and 9 indicates a strain gauge measurement sample.
Claims (3)
ルファス相と微結晶相とが混在するゲルマニウム薄膜
と，該薄膜に電流を入出力するための一対の電極とを備
え，前記薄膜が少なくとも30S・cm-1以上の導電率を有
することを特徴とするゲルマニウム薄膜ｎ形導電体。An insulating substrate, a germanium thin film formed on the substrate and having an amorphous phase and a microcrystalline phase mixed therein, and a pair of electrodes for inputting and outputting a current to and from the thin film. Has a conductivity of at least 30 S · cm −1 or more.
上の負の極性を示す熱電能を有することを特徴とする請
求項１記載のゲルマニウム薄膜ｎ形導電体。2. The germanium thin film n-type conductor according to claim 1, wherein said thin film has a thermoelectric power exhibiting a negative polarity having an absolute value of at least 100 μV / K or more.
ゲルマニウム薄膜を形成する工程と，前記ゲルマニウム
薄膜を，被酸化性ガス雰囲気中で300℃ないし600℃で、
その常温導電率が30S・cm-1に定着するまで熱アニール
する工程とからなる請求項１記載のゲルマニウム薄膜ｎ
形導電体の製造方法。3. A step of forming a germanium thin film of an amorphous phase containing a group V element on a substrate, and forming the germanium thin film at 300 ° C. to 600 ° C. in an oxidizing gas atmosphere.
2. The germanium thin film n according to claim 1, further comprising a step of thermal annealing until the room temperature conductivity is fixed to 30 S · cm −1.
Manufacturing method of shaped conductor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1077755A JP2645586B2 (en) | 1989-03-29 | 1989-03-29 | Germanium thin film n-type conductor and method of manufacturing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1077755A JP2645586B2 (en) | 1989-03-29 | 1989-03-29 | Germanium thin film n-type conductor and method of manufacturing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02256282A JPH02256282A (en) | 1990-10-17 |
| JP2645586B2 true JP2645586B2 (en) | 1997-08-25 |
Family
ID=13642750
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1077755A Expired - Fee Related JP2645586B2 (en) | 1989-03-29 | 1989-03-29 | Germanium thin film n-type conductor and method of manufacturing the same |
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| Country | Link |
|---|---|
| JP (1) | JP2645586B2 (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0630343B2 (en) * | 1985-12-28 | 1994-04-20 | アンリツ株式会社 | Amorphous silicon thin film conductor containing microcrystalline phase |
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1989
- 1989-03-29 JP JP1077755A patent/JP2645586B2/en not_active Expired - Fee Related
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