JPH0547482B2 - - Google Patents
Info
- Publication number
- JPH0547482B2 JPH0547482B2 JP63303817A JP30381788A JPH0547482B2 JP H0547482 B2 JPH0547482 B2 JP H0547482B2 JP 63303817 A JP63303817 A JP 63303817A JP 30381788 A JP30381788 A JP 30381788A JP H0547482 B2 JPH0547482 B2 JP H0547482B2
- Authority
- JP
- Japan
- Prior art keywords
- materials
- present
- metal chalcogenide
- metal
- element selected
- 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 - Lifetime
Links
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 7
- 229910052711 selenium Inorganic materials 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 229910052714 tellurium Inorganic materials 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 150000004770 chalcogenides Chemical class 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- 230000003287 optical effect Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052798 chalcogen Inorganic materials 0.000 description 2
- 150000001787 chalcogens Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G1/00—Methods of preparing compounds of metals not covered by subclasses C01B, C01C, C01D, or C01F, in general
- C01G1/12—Sulfides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/20—Methods for preparing sulfides or polysulfides, in general
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/007—Tellurides or selenides of metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/78—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by stacking-plane distances or stacking sequences
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
（技術分野）
本発明は多元系金属カルコゲナイドに関するも
のである。
（従来技術）
金属カルコゲナイドは、酸素に較べてカルコゲ
ン（Ｓ、Se、Te）の電気陰性度が小さいため、
金属オキサイドに較べてイオン性が小さく共有結
合性が大きい。それ故、本質的に結合の異方性が
大きく、低次元性（層状、鎖状、チヤンネル構造
等）の物質を形成し易い。また、物性的にはカル
コゲンの電子の最高被占準位が酸素のそれよりも
浅いために、オキサイドが、主として絶縁体やバ
ンドギヤキヤツプの大きい半導体を形成するのに
対し、カルコゲナイドは、良電導体やバンドギヤ
ツプの小さい半導体を形成しやすい。金属カルコ
ゲナイドはこれらの構造的、物性的特徴を生かし
て、光学材料（太陽電池、非線型光学材料、発光
材料）、超電導材料（特にシエブレル化合物）、リ
チウム電池材料等への幅広い応用が期待され、既
に一部は実用化されている。
現在実用に供されているセラミツクス材料の大
半はオキサイドであるが、今後素材・材料に対す
る要求が益々多様化していく中にあつて、前述し
たようにオキサイドにない特徴を持つ金属カルコ
ゲナイドを、素材・材料として開拓する必要性は
更に高まると予想される。その場合に重要なこと
は、物質群（化合物群）の数を多くそろえること
であるが、三元系（金属二種）以上の金属カルコ
ゲナイドは、チオスピネル、カルコパライト、シ
エブレル等２〜３の物質群を形成することが知ら
れているだけである。
（発明の課題）
そこで、本発明は金属を多種含む新規な金属カ
ルコゲナイドを提供することをその課題とする。
（課題を解決するための手段）
本発明者は、前記課題を解決すべく種々研究を
重ねた結果、本発明を完成するに至つた。
即ち、本発明によれば、下記一般式（）で表
わされる組成を有する新規な多元系金属カルコゲ
ナイドが提供される。これらのものは殆んど同一
の結晶構造を有するものである。
一般式（）
A(1-a)xA′axByCz
（式中、ＡはBi又はSb、A′はPb、Sn及びGeの
中から選ばれる少なくとも１種の元素、ＢはTi、
Ｖ、Nb及びTaの中から選ばれる少なくとも１種
の元素、ＣはＳ、Se及びTeの中から選ばれる少
なくとも１種の元素を示し、ａは０＜ａ＜１の
数、ｘは0.8≦ｘ≦1.2の数、ｙは0.8≦ｙ≦1.2の
数、ｚは2.4≦ｚ≦3.6の数を示す）
本発明の多元系金属カルコゲナイドは、前記組
成に対応する成分の元素粉末あるいは金属カルコ
ゲナイド粉末を、その組成割合に秤取して、石英
等の耐熱耐酸化性容器中に真空封入し、400〜
1200℃で加熱処理した後室温まで冷却することに
よつて製造することができる。
このようにして得られたものは、褐色から黒色
の粉末で、粉末Ｘ線回析パターンが殆ど１つの面
からの回折線のみを示す。また条件によつて簿片
状結晶が得られ、それが容易に劈開することとあ
わせ、何らかの層状構造を持つと推定される。
また、本発明の金属カルコゲナイドの場合、成
分Ａ、A′、Ｂ、Ｃをそれぞれ一定の範囲で複合
化（固溶化）させることが可能である。
（発明の効果）
本発明の多元系金属カルコゲナイドは、太陽電
池、非線型光学材料、発光材料等の光学材料や、
超電導材料、リチウム電池材料等として利用され
る。
（実施例）
次に本発明を実施例によりさらに詳細に説明す
る。
実施例 １
前記一般式（）の組成に対応する金属カルコ
ゲナイドを次のようにして合成した。
表−１の組成に対応する元素粉末をその組成割
合に採取し、石英容器中に真空封入した後、400
〜1200℃の温度に加熱し、次いで室温まで冷却し
た。
このようにして得られた金属カルコゲナイドの
具体的組成と、その粉末Ｘ線回折パターンにおけ
る主な回折線の面間隔（Å）を表−１に示す。
(Technical Field) The present invention relates to multi-component metal chalcogenides. (Prior art) In metal chalcogenides, because the electronegativity of chalcogen (S, Se, Te) is lower than that of oxygen,
Compared to metal oxides, it has less ionicity and more covalent bonding. Therefore, the anisotropy of bonding is essentially large, and it is easy to form a substance with low dimensionality (layered, chained, channel structure, etc.). In addition, in terms of physical properties, the highest occupied level of chalcogen electrons is shallower than that of oxygen, so oxides mainly form insulators and semiconductors with large band gear caps, whereas chalcogenides are It is easy to form conductors and semiconductors with small band gaps. Taking advantage of these structural and physical characteristics, metal chalcogenides are expected to have a wide range of applications such as optical materials (solar cells, nonlinear optical materials, light-emitting materials), superconducting materials (particularly Siebrel compounds), and lithium battery materials. Some of them have already been put into practical use. The majority of ceramic materials currently in practical use are oxides, but as requirements for materials become more and more diversified in the future, metal chalcogenides, which have characteristics not found in oxides, are being developed as materials. It is expected that the need to develop it as a material will further increase. In that case, the important thing is to have a large number of substance groups (compound groups), but metal chalcogenides of ternary system (two types of metals) or more have two or three substance groups such as thiospinel, chalcopalite, and siebrel. It is only known to form. (Problem of the Invention) Therefore, an object of the present invention is to provide a novel metal chalcogenide containing various metals. (Means for Solving the Problems) The present inventor has completed various studies to solve the above problems, and as a result, has completed the present invention. That is, according to the present invention, a novel multi-component metal chalcogenide having a composition represented by the following general formula () is provided. These materials have almost the same crystal structure. General formula () A (1-a)x A′ ax ByCz (wherein, A is Bi or Sb, A′ is at least one element selected from Pb, Sn, and Ge, B is Ti,
At least one element selected from V, Nb and Ta, C represents at least one element selected from S, Se and Te, a is a number of 0<a<1, x is 0.8≦ The multi-component metal chalcogenide of the present invention is an elemental powder or metal chalcogenide powder of components corresponding to the above composition. Weigh out the composition ratio, vacuum seal it in a heat-resistant and oxidation-resistant container such as quartz, and
It can be produced by heating at 1200°C and then cooling to room temperature. The product thus obtained is a brown to black powder whose powder X-ray diffraction pattern shows almost only diffraction lines from one plane. Also, depending on the conditions, flaky crystals can be obtained, which can be easily cleaved, and it is assumed that they have some kind of layered structure. Further, in the case of the metal chalcogenide of the present invention, it is possible to form a composite (solid solution) of each of the components A, A', B, and C within a certain range. (Effects of the Invention) The multi-component metal chalcogenide of the present invention can be used in optical materials such as solar cells, nonlinear optical materials, and luminescent materials;
Used as superconducting material, lithium battery material, etc. (Example) Next, the present invention will be explained in more detail with reference to Examples. Example 1 A metal chalcogenide corresponding to the composition of the above general formula () was synthesized as follows. Elemental powders corresponding to the compositions in Table 1 were collected in the proportions, vacuum-sealed in a quartz container, and then
Heated to a temperature of ~1200°C and then cooled to room temperature. Table 1 shows the specific composition of the metal chalcogenide thus obtained and the interplanar spacing (Å) of the main diffraction lines in its powder X-ray diffraction pattern.
【表】【table】
Claims (1)
中から選ばれる少なくとも１種の元素、ＢはTi、
Ｖ、Nb及びTaの中から選ばれる少なくとも１種
の元素、ＣはＳ、Se及びTeの中から選ばれる少
なくとも１種の元素を示し、ａは０＜ａ＜１の
数、ｘは0.8≦ｘ≦1.2の数、ｙは0.8≦ｙ≦1.2の
数、ｚは2.4≦ｚ≦3.6の数を示す）で表わされる
組成を有することを特徴とする多元素金属カルゲ
ナイド。[Claims] 1 General formula A (1-a)x A' ax ByCz (wherein A is Bi or Sb, A' is at least one element selected from Pb, Sn and Ge, B is Ti,
At least one element selected from V, Nb and Ta, C represents at least one element selected from S, Se and Te, a is a number of 0<a<1, x is 0.8≦ A multi-element metal calgenide characterized by having a composition represented by x≦1.2, y a number 0.8≦y≦1.2, and z a number 2.4≦z≦3.6.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63303817A JPH02149406A (en) | 1988-11-30 | 1988-11-30 | Multicomponent metal chalcogenide |
| US07/446,548 US5051204A (en) | 1988-11-30 | 1989-11-28 | Multi-element metal chalocogenide |
| EP89312411A EP0371780B1 (en) | 1988-11-30 | 1989-11-29 | Multi-element metal chalcogenide |
| DE89312411T DE68908108T2 (en) | 1988-11-30 | 1989-11-29 | Multi-element metal chalcogenide. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63303817A JPH02149406A (en) | 1988-11-30 | 1988-11-30 | Multicomponent metal chalcogenide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02149406A JPH02149406A (en) | 1990-06-08 |
| JPH0547482B2 true JPH0547482B2 (en) | 1993-07-16 |
Family
ID=17925662
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63303817A Granted JPH02149406A (en) | 1988-11-30 | 1988-11-30 | Multicomponent metal chalcogenide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02149406A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0745303A (en) * | 1993-07-30 | 1995-02-14 | Yoshihiro Onishi | Chargeable power supply device |
| JP5664981B2 (en) * | 2012-10-05 | 2015-02-04 | 国立大学法人東京工業大学 | Superconducting compound and its production method |
-
1988
- 1988-11-30 JP JP63303817A patent/JPH02149406A/en active Granted
Non-Patent Citations (1)
| Title |
|---|
| CHEMICAL ABSTRACTS=1975 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02149406A (en) | 1990-06-08 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |