JP2013079178A - Method for forming graphite thin film - Google Patents
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- JP2013079178A JP2013079178A JP2011221122A JP2011221122A JP2013079178A JP 2013079178 A JP2013079178 A JP 2013079178A JP 2011221122 A JP2011221122 A JP 2011221122A JP 2011221122 A JP2011221122 A JP 2011221122A JP 2013079178 A JP2013079178 A JP 2013079178A
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- 239000010409 thin film Substances 0.000 title claims abstract description 120
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 67
- 239000010439 graphite Substances 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 57
- 239000000758 substrate Substances 0.000 claims abstract description 56
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 45
- 238000010438 heat treatment Methods 0.000 claims abstract description 32
- 239000002184 metal Substances 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 238000005240 physical vapour deposition Methods 0.000 claims abstract description 9
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 8
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000004544 sputter deposition Methods 0.000 claims description 23
- 239000004215 Carbon black (E152) Substances 0.000 claims description 7
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 238000000859 sublimation Methods 0.000 claims description 2
- 230000008022 sublimation Effects 0.000 claims description 2
- 238000012546 transfer Methods 0.000 abstract description 7
- 238000000151 deposition Methods 0.000 abstract description 6
- 238000005530 etching Methods 0.000 description 18
- 238000001069 Raman spectroscopy Methods 0.000 description 17
- 239000007789 gas Substances 0.000 description 15
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- 238000012545 processing Methods 0.000 description 9
- 238000005259 measurement Methods 0.000 description 7
- 238000001237 Raman spectrum Methods 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 229910021389 graphene Inorganic materials 0.000 description 4
- 238000007865 diluting Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- -1 graphite (laminated graphene Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005477 sputtering target Methods 0.000 description 1
- 238000013518 transcription Methods 0.000 description 1
- 230000035897 transcription Effects 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
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- Physical Vapour Deposition (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
Description
本発明は、グラファイト薄膜の形成方法に関する。 The present invention relates to a method for forming a graphite thin film.
近年、新しい電子材料としてグラフェン、及びその積層体であるグラファイト薄膜に注目が集まっている。グラファイト薄膜の形成方法としては、以下の（１）、（２）の方法が提案されている（特許文献１参照）。
（１）基板上にグラフェンを形成するための金属触媒を用意し、加熱した金属触媒へ炭素を含むガスを供給し、金属触媒上で反応させて炭素を析出させる方法。
（２）基板上にグラフェンを形成するための金属触媒を用意し、加熱した金属触媒へ炭素を含むガスを供給し、金属触媒中に炭素を固溶させ、金属触媒を冷却する過程で金属触媒表面に炭素を析出させる方法。
In recent years, attention has been focused on graphene as a new electronic material and a graphite thin film that is a laminate thereof. As a method for forming a graphite thin film, the following methods (1) and (2) have been proposed (see Patent Document 1).
(1) A method of preparing a metal catalyst for forming graphene on a substrate, supplying a gas containing carbon to the heated metal catalyst, and causing the reaction on the metal catalyst to deposit carbon.
(2) Preparing a metal catalyst for forming graphene on the substrate, supplying a gas containing carbon to the heated metal catalyst, dissolving the carbon in the metal catalyst, and cooling the metal catalyst A method of depositing carbon on the surface.
特許文献１記載の方法により形成されたグラファイト薄膜は金属上にあり、このままでは電子デバイスへ応用し難い。そのため、金属上にあるグラファイト薄膜を、シリコン等の基板へ転写する提案がなされている（特許文献２参照）。 The graphite thin film formed by the method described in Patent Document 1 is on a metal and is difficult to apply to an electronic device as it is. Therefore, a proposal has been made to transfer a graphite thin film on a metal to a substrate such as silicon (see Patent Document 2).
しかしながら、グラファイト薄膜を転写する過程において、グラファイト薄膜にしわが生じたり、未転写部分が発生する等、グラファイト薄膜に欠陥を誘起してしまう。
本発明は以上の点に鑑みなされたものであり、転写を必ずしも必要としない、グラファイト薄膜の形成方法を提供することを目的とする。
However, in the process of transferring the graphite thin film, defects are induced in the graphite thin film, such as wrinkles in the graphite thin film and untransferred portions.
This invention is made | formed in view of the above point, and it aims at providing the formation method of a graphite thin film which does not necessarily require transcription | transfer.
本発明のグラファイト薄膜の形成方法は、物理気相堆積法により、（ａ）炭素と（ｂ）金属又はゲルマニウムとを含む薄膜Ａを基板上に形成し、熱処理により炭素を基板上に析出させ、（ｂ）成分を除去し、基板上にグラファイト薄膜を形成する。本発明によれば、転写を行わなくても、グラファイト（グラフェンシートの積層体）薄膜を形成することができる。 In the method for forming a graphite thin film of the present invention, a thin film A containing (a) carbon and (b) metal or germanium is formed on a substrate by physical vapor deposition, and carbon is deposited on the substrate by heat treatment, (B) The component is removed, and a graphite thin film is formed on the substrate. According to the present invention, a graphite (laminated graphene sheet) thin film can be formed without transferring.
本発明のグラファイト薄膜の形成方法における各段階を図示すると、図１に示すとおりとなる。図１の（１）は、使用する基板１を示す。図１の（２）は、基板１の上に、物理気相堆積法により、炭素原子３、（ｂ）成分の原子５が堆積し、薄膜Ａ（符号７）を形成している状態を示す。このとき、（ｂ）成分が金属であると、薄膜Ａは金属炭素混合膜となる。図１の（３）は熱処理後、グラファイト薄膜９が基板上に析出している状態を示す。このとき、グラファイト薄膜９の上には、（ｂ）成分の層１１が残存している。図１の（４）は、（ｂ）成分の層１１を除去し、基板１上にグラファイト薄膜９が形成されている状態を示す。 Each stage in the method for forming a graphite thin film of the present invention is illustrated as shown in FIG. FIG. 1 (1) shows a substrate 1 to be used. (2) of FIG. 1 shows a state in which a carbon atom 3 and an atom 5 of the component (b) are deposited on the substrate 1 by physical vapor deposition to form a thin film A (symbol 7). . At this time, if the component (b) is a metal, the thin film A becomes a metal carbon mixed film. (3) in FIG. 1 shows a state in which the graphite thin film 9 is deposited on the substrate after the heat treatment. At this time, the layer 11 of the component (b) remains on the graphite thin film 9. (4) of FIG. 1 shows a state in which the layer 11 of the component (b) is removed and the graphite thin film 9 is formed on the substrate 1.
前記金属としては、例えば、Fe、Co、Ni、Cu、Pt、Ag等が挙げられる。グラフェンを形成する上で触媒として機能する金属が好ましい。
前記物理気相堆積法（Physical Vapor Deposition）としては、例えば、スパッタ、蒸着等が挙げられる。物理気相堆積法により形成された薄膜Ａは熱的に非平衡な状態にある。
Examples of the metal include Fe, Co, Ni, Cu, Pt, and Ag. A metal that functions as a catalyst in forming graphene is preferred.
Examples of the physical vapor deposition method include sputtering and vapor deposition. The thin film A formed by physical vapor deposition is in a thermally non-equilibrium state.
薄膜Ａを形成する方法としては、例えば、炭素を含むガス中で、（ｂ）成分をスパッタする方法が挙げられる。この炭素を含むガスとしては、例えば、炭化水素(例えば、メタン、エタン、エチレン等)を含むガスが挙げられる。この方法によれば、スパッタガスに由来する炭素と、スパッタターゲットに由来する（ｂ）成分とを含む薄膜Ａを形成することができる。 Examples of the method for forming the thin film A include a method of sputtering the component (b) in a gas containing carbon. Examples of the gas containing carbon include a gas containing a hydrocarbon (for example, methane, ethane, ethylene, etc.). According to this method, it is possible to form the thin film A including carbon derived from the sputtering gas and the component (b) derived from the sputtering target.
また、薄膜Ａを形成する別の方法としては、スパッタ装置に、（ｂ）成分のターゲットとともに、炭素（例えばグラファイト）のターゲットも取り付け、同時スパッタにより、（ｂ）成分と炭素とを含む薄膜Ａを形成する方法がある。また、炭素を（ｂ）成分に加えたものをターゲットとして、（ｂ）成分と炭素とを含む薄膜Ａを形成する方法もある。 As another method of forming the thin film A, a thin film A containing the component (b) and carbon is attached to the sputtering apparatus by attaching a carbon (for example, graphite) target together with the component (b) target. There is a method of forming. There is also a method of forming the thin film A containing the component (b) and carbon by using a target obtained by adding carbon to the component (b).
前記熱処理における熱処理温度は、（ｂ）成分の融点より低いことが好ましい。このことは、例えば基板と（ｂ）成分との不要な反応を抑制する点で有利である。熱処理は、高真空下で行ってもよいし、不活性ガス雰囲気（常圧又は減圧）下で行ってもよい。 The heat treatment temperature in the heat treatment is preferably lower than the melting point of the component (b). This is advantageous in that, for example, an unnecessary reaction between the substrate and the component (b) is suppressed. The heat treatment may be performed under a high vacuum, or may be performed under an inert gas atmosphere (normal pressure or reduced pressure).
前記（ｂ）成分を除去する方法としては、例えば、熱処理後、（ｂ）成分を可溶な液体と接触させることで、前記（ｂ）成分を除去する方法が挙げられる。（ｂ）成分を可溶な液体は特に限定されず、例えば、無機酸（硫酸、硝酸、塩酸等）を用いることができる。 Examples of the method for removing the component (b) include a method for removing the component (b) by bringing the component (b) into contact with a soluble liquid after heat treatment. The liquid in which the component (b) is soluble is not particularly limited, and for example, an inorganic acid (sulfuric acid, nitric acid, hydrochloric acid, etc.) can be used.
また、前記（ｂ）成分がゲルマニウムである場合は、（ｂ）成分を除去する方法として、例えば、１Ｐａ以上の圧力下で熱処理を行う方法が挙げられる。この場合、ゲルマニウムが雰囲気中の酸素と反応し酸化ゲルマニウムとなり昇華することで除去される。ゲルマニウムを昇華させる熱処理は、炭素を基板上に析出させる熱処理時であってもよいし、それとは別の炭素の析出後の熱処理であってもよい。 When the component (b) is germanium, examples of the method for removing the component (b) include a method of performing a heat treatment under a pressure of 1 Pa or more. In this case, germanium reacts with oxygen in the atmosphere to form germanium oxide, which is removed by sublimation. The heat treatment for sublimating germanium may be at the time of heat treatment for precipitating carbon on the substrate, or may be heat treatment after precipitation of carbon other than that.
本発明の実施形態を図面に基づいて説明する。
＜実施例１＞
１．グラファイト薄膜の形成方法
基板として、シリコンウェハの表面に、熱酸化により酸化膜を形成した物を用いた。この基板を、一般的なマグネトロンスパッタ装置（以下、単にスパッタ装置とする）に取り付けた。スパッタ装置には、Fe（カーボンの固溶度が高い金属、金属触媒）のターゲットを取り付け、スパッタガスとしてメタン（炭化水素）を１０％含むアルゴンガスを導入し、真空度を０．０１ｍｂａｒとした。この条件において、上述した基板上に、スパッタ（物理気相堆積法）により、膜厚２０ｎｍの薄膜Ａを形成した。この薄膜Ａは、メタン由来の炭素とＦｅとを含む薄膜であり、おおよそ２０原子％の炭素を含んでいた。
Embodiments of the present invention will be described with reference to the drawings.
<Example 1>
1. Method for Forming Graphite Thin Film A substrate in which an oxide film was formed on the surface of a silicon wafer by thermal oxidation was used. This substrate was attached to a general magnetron sputtering apparatus (hereinafter simply referred to as a sputtering apparatus). A target of Fe (metal having high solid solubility of carbon, metal catalyst) is attached to the sputtering apparatus, and argon gas containing 10% methane (hydrocarbon) is introduced as a sputtering gas, and the degree of vacuum is set to 0.01 mbar. . Under these conditions, a thin film A having a thickness of 20 nm was formed on the above-described substrate by sputtering (physical vapor deposition method). This thin film A was a thin film containing carbon derived from methane and Fe, and contained approximately 20 atomic% of carbon.
次に、薄膜Ａを形成した基板を、真空度０．７Ｐａ、８００℃の下で、３０分間熱処理した。熱処理後の薄膜をラマン分光測定したところ、図２に示すように、グラファイトの特徴を示すGピークや２Dピークが見られた。また、熱処理後の薄膜を電子顕微鏡観察したところ、図３に示すように、薄片状の膜が観察された。また、表面上に凝集したFe粒子も観察された。ラマン分光結果および電子顕微鏡観察結果より、基板上の薄膜は、２−９層程度のグラファイト薄膜であることが分かった。このグラファイト薄膜は、熱処理により、薄膜Ａから炭素が基板上に析出して形成されたものである。 Next, the substrate on which the thin film A was formed was heat-treated for 30 minutes under a degree of vacuum of 0.7 Pa and 800 ° C. When the thin film after the heat treatment was subjected to Raman spectroscopic measurement, as shown in FIG. 2, G peak and 2D peak indicating the characteristics of graphite were observed. When the thin film after the heat treatment was observed with an electron microscope, a flaky film was observed as shown in FIG. Also, Fe particles aggregated on the surface were observed. From the results of Raman spectroscopy and observation with an electron microscope, it was found that the thin film on the substrate was a graphite thin film of about 2-9 layers. This graphite thin film is formed by depositing carbon on the substrate from the thin film A by heat treatment.
次に、熱処理後の基板を、エッチング液（濃硫酸を純水で１／１０に希釈した液）を用い、室温で２０分間エッチング処理した。エッチング処理後の基板表面をラマン分光測定したところ、図４に示すように、グラファイト薄膜が基板表面に維持されていることが確認できた。また、エッチング処理後の基板表面を電子顕微鏡観察したところ、図５に示すように、Fe粒子が除去されていることが確認できた。なお、Fe粒子が取れ難い場合は、上述したエッチング処理において、超音波を印加しながらエッチングすればよい。 Next, the substrate after the heat treatment was etched at room temperature for 20 minutes using an etching solution (a solution obtained by diluting concentrated sulfuric acid to 1/10 with pure water). As a result of Raman spectroscopic measurement of the substrate surface after the etching treatment, it was confirmed that the graphite thin film was maintained on the substrate surface as shown in FIG. Moreover, when the substrate surface after the etching treatment was observed with an electron microscope, it was confirmed that Fe particles were removed as shown in FIG. If it is difficult to remove Fe particles, etching may be performed while applying ultrasonic waves in the above-described etching process.
２．グラファイト薄膜の形成方法が奏する効果
上記のグラファイト薄膜の形成方法を用いれば、転写を行わなくても、非金属の基板上にグラファイト薄膜を形成することができる。
＜実施例２＞
１．グラファイト薄膜の形成方法
前記実施例１と同様の基板をスパッタ装置に取り付けた。スパッタ装置には、Cu（カーボンをわずかに固溶する金属、金属触媒）のターゲットを取り付け、スパッタガスとしてメタン（炭化水素）を１０％含むアルゴンガスを導入し、真空度を０．０１ｍｂａｒとした。この条件において、上述した基板上に、スパッタ（物理気相堆積法）により、膜厚２０ｎｍの薄膜Ａを形成した。この薄膜Ａは、メタン由来の炭素とCuとを含む薄膜であり、おおよそ４原子％の炭素を含んでいた。
2. Effect of Forming Method of Graphite Thin Film If the above-described method of forming a graphite thin film is used, a graphite thin film can be formed on a non-metallic substrate without performing transfer.
<Example 2>
1. Method for Forming Graphite Thin Film A substrate similar to that in Example 1 was attached to a sputtering apparatus. A Cu (metal that slightly dissolves carbon, metal catalyst) target is attached to the sputtering apparatus, and argon gas containing 10% methane (hydrocarbon) is introduced as a sputtering gas, and the degree of vacuum is set to 0.01 mbar. . Under these conditions, a thin film A having a thickness of 20 nm was formed on the above-described substrate by sputtering (physical vapor deposition method). This thin film A was a thin film containing carbon derived from methane and Cu, and contained approximately 4 atomic% of carbon.
次に、薄膜Ａを形成した基板を、真空度０．７Ｐａ、５００℃の下で、３０分間熱処理した。熱処理後の薄膜をラマン分光測定したところ、図６に示すように、グラファイトの特徴を示すGピークが見られた。また、熱処理後の薄膜を電子顕微鏡観察したところ、図７に示すように、薄片状の膜が観察された。また、表面上に凝集したCu粒子も観察された。ラマン分光結果および電子顕微鏡観察結果より、基板上の薄膜は、グラファイト薄膜であることが分かった。このグラファイト薄膜は、熱処理により、薄膜Ａから炭素が基板上に析出して形成されたものである。 Next, the substrate on which the thin film A was formed was heat-treated for 30 minutes under a degree of vacuum of 0.7 Pa and 500 ° C. When the thin film after the heat treatment was subjected to Raman spectroscopic measurement, as shown in FIG. 6, a G peak indicating the characteristics of graphite was observed. Further, when the thin film after the heat treatment was observed with an electron microscope, a flaky film was observed as shown in FIG. In addition, Cu particles aggregated on the surface were also observed. From the results of Raman spectroscopy and electron microscope observation, it was found that the thin film on the substrate was a graphite thin film. This graphite thin film is formed by depositing carbon on the substrate from the thin film A by heat treatment.
次に、熱処理後の基板を、エッチング液（濃硫酸を純水で１／１０に希釈した液）を用い、室温で４０分間エッチング処理した。エッチング処理後の基板表面をラマン分光測定したところ、図８に示すように、グラファイト薄膜が基板表面に維持されていることが確認できた。また、エッチング処理後の基板表面を電子顕微鏡観察したところ、図９に示すように、Cu粒子が除去されていることが確認できた。なお、Cu粒子が取れ難い場合は、上述したエッチング処理において、超音波を印加しながらエッチングすればよい。 Next, the substrate after the heat treatment was etched for 40 minutes at room temperature using an etching solution (a solution obtained by diluting concentrated sulfuric acid to 1/10 with pure water). When the Raman spectroscopic measurement was performed on the substrate surface after the etching treatment, it was confirmed that the graphite thin film was maintained on the substrate surface as shown in FIG. Moreover, when the substrate surface after the etching treatment was observed with an electron microscope, it was confirmed that Cu particles were removed as shown in FIG. In addition, when it is difficult to remove Cu particles, the etching may be performed while applying ultrasonic waves in the above-described etching process.
２．グラファイト薄膜の形成方法が奏する効果
上記のグラファイト薄膜の形成方法を用いれば、転写を行わなくても、非金属の基板上にグラファイト薄膜を形成することができる。
＜実施例３＞
１．グラファイト薄膜の形成方法
前記実施例１と同様の基板をスパッタ装置に取り付けた。スパッタ装置には、Ge（カーボンをわずかに固溶する非金属）のターゲットを取り付け、スパッタガスとしてメタン（炭化水素）を１０％含むアルゴンガスを導入し、真空度を０．０１ｍｂａｒとした。この条件において、上述した基板上に、スパッタ（物理気相堆積法）により、膜厚２０ｎｍの薄膜Ａを形成した。この薄膜Ａは、メタン由来の炭素とGeとを含む薄膜であり、おおよそ１原子％の炭素を含んでいた。
2. Effect of Forming Method of Graphite Thin Film If the above-described method of forming a graphite thin film is used, a graphite thin film can be formed on a non-metallic substrate without performing transfer.
<Example 3>
1. Method for Forming Graphite Thin Film A substrate similar to that in Example 1 was attached to a sputtering apparatus. A Ge (non-metal that slightly dissolves carbon) target was attached to the sputtering apparatus, and argon gas containing 10% methane (hydrocarbon) was introduced as a sputtering gas, and the degree of vacuum was set to 0.01 mbar. Under these conditions, a thin film A having a thickness of 20 nm was formed on the above-described substrate by sputtering (physical vapor deposition method). This thin film A was a thin film containing carbon derived from methane and Ge, and contained approximately 1 atomic% of carbon.
次に、薄膜Ａを形成した基板を、真空度０．７Ｐａ、６００℃の下で、３０分間熱処理した。熱処理後の薄膜をラマン分光測定したところ、図１０に示すように、グラファイトの特徴を示すGピークが見られた。また、熱処理後の薄膜を電子顕微鏡観察したところ、図１１に示すように、薄片状の膜が観察された。また、表面上に凝集したGe粒子も観察された。ラマン分光結果および電子顕微鏡観察結果より、基板上の薄膜は、グラファイト薄膜であることが分かった。このグラファイト薄膜は、熱処理により、薄膜Ａから炭素が基板上に析出して形成されたものである。 Next, the substrate on which the thin film A was formed was heat-treated for 30 minutes under a degree of vacuum of 0.7 Pa and 600 ° C. When the thin film after the heat treatment was subjected to Raman spectroscopic measurement, as shown in FIG. 10, a G peak indicating the characteristics of graphite was observed. When the thin film after the heat treatment was observed with an electron microscope, a flaky film was observed as shown in FIG. Further, Ge particles aggregated on the surface were also observed. From the results of Raman spectroscopy and electron microscope observation, it was found that the thin film on the substrate was a graphite thin film. This graphite thin film is formed by depositing carbon on the substrate from the thin film A by heat treatment.
次に、熱処理後の基板を、エッチング液（濃硫酸を純水で１／１０に希釈した液）を用い、室温で４０分間エッチング処理した。エッチング処理後の基板表面をラマン分光測定したところ、グラファイト薄膜が基板表面に維持されていることが確認できた。また、エッチング処理後の基板表面を電子顕微鏡観察したところ、Ge粒子が除去されていることが確認できた。 Next, the substrate after the heat treatment was etched for 40 minutes at room temperature using an etching solution (a solution obtained by diluting concentrated sulfuric acid to 1/10 with pure water). When the Raman spectroscopic measurement was performed on the substrate surface after the etching treatment, it was confirmed that the graphite thin film was maintained on the substrate surface. Moreover, when the substrate surface after the etching treatment was observed with an electron microscope, it was confirmed that Ge particles were removed.
２．グラファイト薄膜の形成方法が奏する効果
上記のグラファイト薄膜の形成方法を用いれば、転写を行わなくても、非金属の基板上にグラファイト薄膜を形成することができる。
＜実施例４＞
１．グラファイト薄膜の形成方法
前記実施例３と同様に、基板上に薄膜Ａを形成した。次に、薄膜Ａを形成した基板を、真空度２Ｐａ、６００℃の下で、３０分間熱処理した。熱処理後の薄膜をラマン分光測定したところ、図１２に示すように、グラファイトの特徴を示すGピークが見られた。また、熱処理後の薄膜を電子顕微鏡観察したところ、図１３に示すように、薄片状の膜が観察された。一方、Ge粒子は見られなかった。熱処理の工程において、雰囲気中の酸素とGeとが反応して酸化ゲルマニウムとなり昇華したためであると考えられる。ラマン分光結果および電子顕微鏡観察結果より、基板上の薄膜は、グラファイト薄膜であることが分かった。このグラファイト薄膜は、熱処理により、薄膜Ａから炭素が基板上に析出して形成されたものである。
2. Effect of Forming Method of Graphite Thin Film If the above-described method of forming a graphite thin film is used, a graphite thin film can be formed on a non-metallic substrate without performing transfer.
<Example 4>
1. Method for Forming Graphite Thin Film Similarly to Example 3, a thin film A was formed on a substrate. Next, the substrate on which the thin film A was formed was heat-treated for 30 minutes under a degree of vacuum of 2 Pa and 600 ° C. When the thin film after the heat treatment was subjected to Raman spectroscopic measurement, as shown in FIG. 12, a G peak indicating the characteristics of graphite was observed. When the thin film after the heat treatment was observed with an electron microscope, a flaky film was observed as shown in FIG. On the other hand, Ge particles were not seen. This is probably because oxygen and Ge in the atmosphere reacted in the heat treatment step to form germanium oxide and sublimate. From the results of Raman spectroscopy and electron microscope observation, it was found that the thin film on the substrate was a graphite thin film. This graphite thin film is formed by depositing carbon on the substrate from the thin film A by heat treatment.
２．グラファイト薄膜の形成方法が奏する効果
上記のグラファイト薄膜の形成方法を用いれば、転写を行わなくても、非金属の基板上にグラファイト薄膜を形成することができる。また、上記のグラファイト薄膜の形成方法によれば、エッチング処理を行わなくても、Geを除去することができる。
2. Effect of Forming Method of Graphite Thin Film If the above-described method of forming a graphite thin film is used, a graphite thin film can be formed on a non-metallic substrate without performing transfer. Further, according to the above method for forming a graphite thin film, Ge can be removed without performing an etching process.
尚、本発明は前記実施の形態になんら限定されるものではなく、本発明を逸脱しない範囲において種々の態様で実施しうることはいうまでもない。
例えば、前記実施例１において、スパッタ装置に、Feのターゲットの代わりに、Co、Ni、又はそれらの合金（炭素を固溶する金属）のターゲットを取り付け、CoやNiと炭素とを
含む薄膜Ａを形成してもよい。この場合でも、前記実施例１と同様に、グラファイト薄膜を形成することができる。
In addition, this invention is not limited to the said embodiment at all, and it cannot be overemphasized that it can implement with a various aspect in the range which does not deviate from this invention.
For example, in the first embodiment, instead of the Fe target, a target of Co, Ni, or an alloy thereof (metal that dissolves carbon) is attached to the sputtering apparatus, and the thin film A containing Co, Ni, and carbon is attached. May be formed. Even in this case, a graphite thin film can be formed as in the first embodiment.
また、前記実施例２において、スパッタ装置に、Cuのターゲットの代わりに、Pt、Ag、又はそれらの合金（炭素をわずかに固溶する金属）のターゲットを取り付け、PtやAgと炭素とを含む薄膜Ａを形成してもよい。この場合でも、前記実施例２と同様に、グラファイト薄膜を形成することができる。 In the second embodiment, instead of the Cu target, a target of Pt, Ag, or an alloy thereof (a metal that slightly dissolves carbon) is attached to the sputtering apparatus, and includes Pt, Ag, and carbon. The thin film A may be formed. Even in this case, a graphite thin film can be formed as in the second embodiment.
また、前記実施例１〜４において、スパッタ装置に、金属のターゲットとともに、炭素（例えばグラファイト）のターゲットも取り付け、同時スパッタにより、金属と炭素とを含む薄膜Ａを形成してもよい。この場合でも、前記実施例１〜４と同様に、グラファイト薄膜を形成することができる。なお、上記の場合におけるスパッタガスは、アルゴンのみであってもよいし、アルゴンと炭化水素との混合ガスであってもよい。 Further, in Examples 1 to 4, a thin film A containing metal and carbon may be formed by simultaneous sputtering, with a carbon (for example, graphite) target attached to the sputtering apparatus. Even in this case, the graphite thin film can be formed as in the first to fourth embodiments. Note that the sputtering gas in the above case may be only argon or a mixed gas of argon and hydrocarbon.
また、前記実施例１〜４において、スパッタガスに含まれる炭化水素は、エタン、エチレン等であってもよい。
また、前記実施例１〜３において、熱処理は、大気圧不活性ガス中で行ってもよいし、６００℃以下の大気中で行ってもよい。この場合でも、前記実施例１〜３と同様に、グラファイト薄膜を基板上に形成することができる。
In Examples 1 to 4, the hydrocarbon contained in the sputtering gas may be ethane, ethylene, or the like.
Moreover, in the said Examples 1-3, heat processing may be performed in an atmospheric pressure inert gas, and may be performed in the atmosphere below 600 degreeC. Even in this case, the graphite thin film can be formed on the substrate as in the first to third embodiments.
１・・・基板、３・・・炭素原子、５・・・（ｂ）成分の原子、７・・・薄膜Ａ
９・・・グラファイト薄膜、１１・・・（ｂ）成分の層
DESCRIPTION OF SYMBOLS 1 ... Substrate, 3 ... Carbon atom, 5 ... (b) Component atom, 7 ... Thin film A
9 ... graphite thin film, 11 ... layer of component (b)
Claims (6)
１Ｐａ以上の圧力下で前記熱処理を行うことで、ゲルマニウムを昇華により除去することを特徴とする請求項１〜５のいずれか１項記載のグラファイト薄膜の形成方法。 The component (b) is germanium,
The method for forming a graphite thin film according to any one of claims 1 to 5, wherein germanium is removed by sublimation by performing the heat treatment under a pressure of 1 Pa or more.
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