JPS5912503A - Method of producing solid electrolyte thin film - Google Patents

Abstract

(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

【発明の詳細な説明】 〔発明の技術分野〕 本発明はリチウムイオン導電性を有する固体電解質薄膜
の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to a method for manufacturing a solid electrolyte thin film having lithium ion conductivity.

〔発明の技術的背景とその問題点〕[Technical background of the invention and its problems]

最近、固体電解質材料への関心が高まってきており、特
にアルカリイオン導電性の固体電解質は、Ｎａ−８％池
、Ｌｉ電池等の電解質としての応用が注目されている。Recently, interest in solid electrolyte materials has increased, and in particular, alkali ion conductive solid electrolytes are attracting attention for their application as electrolytes for Na-8% batteries, Li batteries, and the like.

近年、電子機器の小型化、薄型化、高性能化に伴い、薄
膜型のＬｉ電池等が特に関心を集めている。又、イオン
導電体を用いたデバイスと半導体ＩＣ回路との整合性を
考慮した場合に、固体電解質材料の薄膜化、微細・臂タ
ーン化の必要がある。ｒｃ回路との整合性となると、Ｉ
Ｃに使用されている基板、例えばシリコン、サファイア
、スピネル等の基板上への固体電解質材料の形成が望ま
れている。In recent years, as electronic devices have become smaller, thinner, and more sophisticated, thin-film Li batteries and the like have attracted particular attention. Furthermore, when considering the compatibility between devices using ionic conductors and semiconductor IC circuits, it is necessary to make the solid electrolyte material thinner, finer, and more rounded. When it comes to compatibility with the rc circuit, I
It is desirable to form solid electrolyte materials on substrates used in C, such as silicon, sapphire, spinel, and the like.

しかしながら、従来、固体電解質材料については主に、
セラミック技・術で作られる焼結体がほとんどであるた
め、小型、薄型にすることには限界があり、しかも半導
体ＩＣとの整合性も悪いという欠点があった。However, conventionally, solid electrolyte materials mainly
Since most of them are sintered bodies made using ceramic technology, there is a limit to how small and thin they can be made, and they also have the drawback of poor compatibility with semiconductor ICs.

〔発明の目的〕[Purpose of the invention]

本発明は薄膜型Ｌｉ電池の実現や半導体デバイスとイオ
ン導電体との結合性を可能にした固体電解質薄膜の製造
方法を提供しようとするものである。The present invention aims to provide a method for manufacturing a solid electrolyte thin film that enables the realization of a thin film type Li battery and the bondability between a semiconductor device and an ionic conductor.

〔発明の概要〕[Summary of the invention]

本発明者はＬ１４Ｇｏｏ４−Ｚｎ２Ｇｅ０４系固溶体の
−っで、Ｌｉ３ＰＯ４のγ。相と同じ構造をとるＬｉ４
（、−ｘ）Ｚｎ２ＸＧｅ０４なる組成式のリシコン（す
ｔｈｉｕｍ　５Ｂｐ＠ｒ−ｐＯｎｆＱ　Ｃｏｎｄｕｃｔ
ｏｒ　ｑ　ＬＩＳＩＣＯＮ）に着目し、前記組成式のＸ
が０．０９≦Ｘ≦０．４０の範囲にあるリシコンを高周
波スパッタリング法又は蒸着法によりシリコン、サファ
イア、スピネル等の基板上に形成することによって、γ
１構造をもつリチウムイオン導電性の固体電解質薄膜を
容易に製造し得る方法を見い出したものである。The present inventor has determined the γ of Li3PO4 in the L14Goo4-Zn2Ge04 solid solution. Li4 has the same structure as the phase
(, -x) Zn2XGe04 composition formula (Sthium 5Bp@r-pOnfQ Conduct
or q LISICON), and
By forming γ in the range of 0.09≦X≦0.40 on a substrate of silicon, sapphire, spinel, etc. by high frequency sputtering or vapor deposition,
We have discovered a method for easily manufacturing a lithium ion conductive solid electrolyte thin film having one structure.

次に、本発明の詳細な説明する。Next, the present invention will be explained in detail.

実施例１ まず、Ｌｉ５Ｚｎｏ、５ＧｅＯ４（ｘ＝０．２５）の組
成式で表わされるＬＩＳＪＣＯＮ系材料をターゲットと
し、高周波スパッタリング法によりサファイア基板のＲ
面（１１０２）に厚さ０．３屡の薄膜を形成した。スパ
ッタリングの条件は、基板温度８０°Ｃ１雰囲気ガスＡ
ｒ／Ｃ）ｚ　（酸素７４．６％）、真空度８Ｘ１０−２
Ｔｏｒｒ　、、・やワー１００Ｗで行った。薄膜形成後
、６２０°Ｃで６時間熱処理して結晶性の向上を図った
０ 得られた固体電解質薄膜の結晶構造をＸ線回折法により
調べた結果、ＬＩＳＩＣＯＮ構泣（Ｌｉ、ＰＯ４数は、
ターケ゛ットの格子定数とほとんど同じであった。この
ＩｊＳＩＣＯＮ系薄膜の基板系内膜向の導電、率は５０
０°Ｃにおいて、２Ｘ１０　　Ω　σ　で、ターゲット
に用いたＬｉ　３Ｚｎ０．５Ｇｅ０４の５００　’Ｃに
おける４電率６．５Ｘ１０　　Ωαに比べて約１／３０
であるが、Ｌ　Ｉ　２　Ｇｅ　ＯｓやＬ１２ＺｎＧｅＯ
４等の薄膜の１０倍の大きさをもつ。また、同相料の基
板依存性は小さく、石英ガラス、等を用いてもほとんど
同様な膜が得られた。Example 1 First, a LISJCON material represented by the composition formula of Li5Zno, 5GeO4 (x=0.25) was targeted, and the R of a sapphire substrate was removed by high-frequency sputtering.
A thin film with a thickness of 0.3 mm was formed on the surface (1102). The sputtering conditions are: substrate temperature: 80°C; atmosphere gas: A.
r/C)z (oxygen 74.6%), vacuum degree 8X10-2
Torr... and power was set at 100W. After forming the thin film, it was heat-treated at 620°C for 6 hours to improve crystallinity.As a result of examining the crystal structure of the obtained solid electrolyte thin film by X-ray diffraction, it was found that LISICON structure (Li, PO4 number,
The lattice constant was almost the same as that of the target. The conductivity rate of this IjSICON thin film toward the inner film of the substrate is 50
At 0°C, 2X10 Ωσ is approximately 1/30 of the 4-electric constant of Li3Zn0.5Ge04 used as a target, which is 6.5X10 Ωα at 500'C.
However, L I 2 Ge Os and L12ZnGeO
It is 10 times larger than a 4th grade thin film. In addition, the dependence of the in-phase material on the substrate is small, and almost the same film was obtained even when using quartz glass or the like.

また、数回のス・母ツタリングによシｚｎ不足になるた
め、これを補なう目的でＬ１３ｚｎｏ５ＧｅＯ４に１０
〜１００　ｍｏ１％のＺｎＯを過剰に加えたターケ９ッ
トを用いて同様にスフ９ツタリングを行なってサファイ
ア基板のＲ面に薄膜を形成した。この場合もＬＩＳＩＣ
ＯＮ構造の薄膜が得られた。ス・！ツタリングの条件は
基板温度が室温から２５０℃の範囲では影響なく、ガス
圧も６×１０　〜１０Ｘ１０−２Ｔｏｒｒ　、　６０〜
１５０　Ｗのｄ’クワ−同様な薄膜が得られた。In addition, since zn is insufficient due to several times of sintering, 10
A thin film was formed on the R surface of the sapphire substrate by similarly performing Suff 9 tuttering using Tarque 9 to which ~100 mo1% of ZnO was added in excess. In this case too, LISIC
A thin film with an ON structure was obtained. vinegar·! The conditions for tsuttering have no effect when the substrate temperature is in the range from room temperature to 250°C, and the gas pressure is 6 x 10 - 10 x 10 -2 Torr, 60 -
A 150 W d'hoe-like thin film was obtained.

実施例２ Ｌｉｓ　ｓ　ｚ　ｎ　ｏ２ｓＧｅ０４　（Ｘ　＝ｏ、　
ｉ　２　ｓ　）をターｒ、）を用い、高周波スパッタリ
ング法によす、サファイア基板（Ｒ面）上に厚さ０７μ
ｎＬの薄膜を作製した。ス・セツタリングの条件は、実
施例１とほとんど同じでおるが、雰囲気ガスの圧力を１
．ＯＸ　Ｉ　０−２Ｔｏｒｒとした。薄膜形成後６２０
℃で６時間熱処理を行い、結晶性の向上を図った。Example 2 Lis s z no2sGe04 (X = o,
A film with a thickness of 07 μm was deposited on a sapphire substrate (R side) using a high-frequency sputtering method using a tar r, ).
A thin film of nL was produced. The conditions for gas settling were almost the same as in Example 1, except that the pressure of the atmospheric gas was reduced to 1.
．． OXI was set at 0-2 Torr. 620 after thin film formation
Heat treatment was performed at ℃ for 6 hours to improve crystallinity.

得られた薄膜の結晶構造は、非常に弱いながらもＬｉ　
２Ｇｅｍ３と思われるピークが混っているが、ＬＩＳＩ
ＣＯＮ構造をとっている。５００℃における導電率は実
施例１に示したものとほとんど同じ大きさであった。Although the crystal structure of the obtained thin film is very weak, Li
There are some peaks that seem to be 2Gem3, but LISI
It has a CON structure. The conductivity at 500° C. was almost the same magnitude as that shown in Example 1.

また、実施例１と同様、Ｌ　ｌ　ｙ、ｓＺ　ｎ　ａ　２
ｓ　Ｇｅ　ＯａにＺｎＯを１０〜１００　ｍｏｌチ象加
したターゲットを用い、６Ｘ１０　〜１０Ｘ１０　　Ｔ
ｏｒｒ　、　６０〜１５０Ｗの・平ワーの条件でスパッ
タリングを行なったところ、同様にＬＩＳＩＣＯＮ構造
の薄膜を得ることができた。Also, as in Example 1, L ly, sZ na 2
Using a target in which 10 to 100 mol of ZnO was added to s Ge Oa, 6X10 to 10X10T
When sputtering was carried out under the condition of normal power of 60 to 150 W, a thin film having a LISICON structure could be similarly obtained.

実施例３ ターケ０ットとして、Ｌｌ　２．８Ｚｎｏ、６ＧｅＯ４
（Ｘ　＝　０．３　）を用い、実施例１と同様な方法で
高周波ス・ぐツタリングを行い膜厚０．６〜１μ７シＬ
の薄膜を作製し、更に実施例１と同様に熱処理を行い、
結晶性を高めその構造を調べた。薄膜の結晶構造は、や
はりＬＩＳＩＣＯＮ構造でおジ、導電率は５００　’Ｃ
で１×１０−３Ω′″１ｄ１であった。Example 3 As target, Ll 2.8Zno, 6GeO4
(X = 0.3), high frequency suction was performed in the same manner as in Example 1 to obtain a film thickness of 0.6 to 1 μ7.
A thin film was prepared, and then heat treated in the same manner as in Example 1,
We increased the crystallinity and investigated its structure. The crystal structure of the thin film is still a LISICON structure, and the conductivity is 500'C.
The resistance was 1×10−3Ω′″1d1.

また、実施例１と同様Ｌ１２．８ｚｎｏ６Ｇｅ０４にＺ
ｎＯを１０〜１５０　ｍｏ１％過剰に加えたターゲット
を用い、同様な真空度、パワーでスパッタリングを行な
ったところ、同様にＬＩＳＩＣＯＮ構造の薄膜を得るこ
とができた。Also, as in Example 1, Z was added to L12.8zno6Ge04.
When sputtering was performed using a target to which 10 to 150 mo1% of nO was added at the same degree of vacuum and power, a thin film having a LISICON structure could be similarly obtained.

実施例４ ターゲットとして、Ｌ　ｉ　２．ａ　Ｚｎ　ｎＢ　Ｇｅ
Ｏ４（ｘ　〜０，４　）を用いて、実施例１と同様な条
件で高周波スパッタリングにより膜厚０，６〜１μｍの
薄膜を作製し熱処理を行った。Ｘ線回折によυ薄膜の結
晶構造を調べた結果、ＬＩＳＩＣＯＮのピークの他に弱
いながらもＬＩ　ＺｎＧｅ０４と思われるピークが混っ
ていた。導電率は５００″Ｃで４×１０　０確であった
。Example 4 As a target, L i 2. a Zn nB Ge
Using O4(x ~ 0,4), a thin film with a thickness of 0.6 to 1 μm was prepared by high frequency sputtering under the same conditions as in Example 1, and heat treated. As a result of examining the crystal structure of the υ thin film by X-ray diffraction, in addition to the LISICON peak, a weak peak believed to be LI ZnGe04 was mixed. The conductivity was 4×100 at 500″C.

実施例５ Ｌ１５Ｚｎ［１５ＧｅＯ４（Ｘ＝０．２５　）に５０％
ＺｎＯを加えたものを蒸着源として、電子ビーム蒸着に
より薄膜形成を行った。１０″’　Ｔｏｒｒの真空度で
、蒸発源の電力を制御し、膜堆積速度を３５０　Ｘ／ｍ
ｌｎとし、基板温度を１００℃として、薄膜を作製した
。高周波スパッタリングの場合と同様に熱処理を行い、
結晶性の向上を図った。結晶構造はＬＩＳＩＣＯＮ構造
であゃ、強度比もスパッタリングによる薄膜とほとんど
同じであった。導電率も実施例１のスパッタリング膜と
同じであった。Example 5 L15Zn [50% in 15GeO4 (X=0.25)
A thin film was formed by electron beam evaporation using ZnO as a evaporation source. At a vacuum level of 10'' Torr, the power of the evaporation source was controlled and the film deposition rate was 350 X/m.
A thin film was produced at a temperature of 100° C. and a substrate temperature of 100° C. Heat treatment is performed in the same way as in the case of high frequency sputtering,
We aimed to improve crystallinity. Since the crystal structure was a LISICON structure, the intensity ratio was almost the same as that of a thin film produced by sputtering. The conductivity was also the same as that of the sputtered film of Example 1.

また、真空度１０−’　〜１０’　Ｔ’ｏｒｒ、基板温
度、室温から３００℃の条件で電子ビーム蒸着を行なっ
ても同様にＬＩＳＩＣＯＮ構造の薄膜を得ることができ
た。Further, even when electron beam evaporation was performed under the conditions of a vacuum degree of 10-' to 10'T'orr and a substrate temperature of room temperature to 300 DEG C., a thin film having a LISICON structure could be similarly obtained.

実施例６ Ｌｉ　、８ＺｎＣＬ６Ｇｅ０４　（ｘ　＝　０．３　）
に２０％ＺｎＯを加えたものを蒸着源とし、実施例５と
同様の条件で電子ビーム蒸着により薄膜を作製した。同
様な熱処理を行うことによりＬＩＳＩＣＯＮ構造の薄月
莞を得た。同様にｘ＝０．０９〜ｘ　＝　０．４の範囲
のＬＩＳＩＣＯＮ系材料に適轟量ＺｎＯを加えた蒸着源
を用いることによりＬＩＳＩＣＯＮ構造の薄膜を得た。Example 6 Li,8ZnCL6Ge04 (x = 0.3)
A thin film was produced by electron beam evaporation under the same conditions as in Example 5, using 20% ZnO as the evaporation source. A thin moon shell with a LISICON structure was obtained by performing a similar heat treatment. Similarly, a thin film having a LISICON structure was obtained by using a deposition source in which a suitable amount of ZnO was added to a LISICON material in the range of x = 0.09 to x = 0.4.

しかして、上記実施例１〜６で述べたｐ口＜、スパッタ
法、蒸着法において、ターダウト、蒸着源に Ｌｉ４（１−、）Ｚｎ２ＸＧｅｍ４＋　ｙＺｎ。Therefore, in the p-type, sputtering, and vapor deposition methods described in Examples 1 to 6 above, Li4(1-,)Zn2XGem4+ yZn is used as the terdoubt and vapor deposition source.

但し　０．０９≦Ｘ≦０．４０ ０≦ｙ≦１．５ を用いてスパッタ条件、蒸着条件を実施ｆｌｕ　１〜６
に記載した範囲で制御することによりＬＩＳＩＣＯＮ構
造の薄膜を得ることができる。However, sputtering conditions and vapor deposition conditions were carried out using 0.09≦X≦0.40 0≦y≦1.5 flu 1 to 6
A thin film having a LISICON structure can be obtained by controlling within the range described in .

また、本発明方法により得られた代表的な固体電解質薄
膜の５００℃における導電率を下ｉ己表に示す。Further, the electrical conductivity at 500° C. of a typical solid electrolyte thin film obtained by the method of the present invention is shown in the table below.

上表よジ得られた固体電解質薄膜は４電率の商いＬｌイ
オン導電性を有することがわかる。From the table above, it can be seen that the obtained solid electrolyte thin film has Ll ion conductivity based on the quadruplicity.

〔発明の効果〕〔Effect of the invention〕

以上詳述した如く、本発明によれば基板上にＬ　Ｉ　Ｓ
　Ｉ　ＣＯＮ構造のリチウムイオン導電性を肩する固体
電解質薄膜を容易に製造でき、もって薄膜型Ｌｌ電池の
実現や、種々の基板を用いた半導体ＩＣとの整合性によ
り被合デバイスの実現を達成できる等顕著な効果を有す
る。As described in detail above, according to the present invention, L I S
It is possible to easily manufacture a solid electrolyte thin film that supports lithium ion conductivity in the ICON structure, which enables the realization of thin-film type L1 batteries and the realization of integrated devices through compatibility with semiconductor ICs using various substrates. etc. have remarkable effects.

Claims (1)

【特許請求の範囲】[Claims] 高周波スノ臂、タリング法又は蒸着法によりＬｉ４（、
−、）Ｚｎ２ＸＧｅ０４　（０，０９≦Ｘ≦０．４０）
の組成式で表わされる材料を基板上に形成することを特
徴とする固体電解質薄膜の製造方法。Li4(,
-,)Zn2XGe04 (0,09≦X≦0.40)
A method for producing a solid electrolyte thin film, comprising forming a material represented by the composition formula on a substrate.