JP6917028B2 - Silver-coated lead tellurium glass powder and its manufacturing method, and conductive paste - Google Patents
Silver-coated lead tellurium glass powder and its manufacturing method, and conductive paste Download PDFInfo
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- JP6917028B2 JP6917028B2 JP2017176555A JP2017176555A JP6917028B2 JP 6917028 B2 JP6917028 B2 JP 6917028B2 JP 2017176555 A JP2017176555 A JP 2017176555A JP 2017176555 A JP2017176555 A JP 2017176555A JP 6917028 B2 JP6917028 B2 JP 6917028B2
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- Prior art keywords
- silver
- glass powder
- lead
- tellurium glass
- coated
- Prior art date
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- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 title claims description 203
- 239000011521 glass Substances 0.000 title claims description 196
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims description 187
- 229910052714 tellurium Inorganic materials 0.000 title claims description 186
- 239000000843 powder Substances 0.000 title claims description 183
- 229910052709 silver Inorganic materials 0.000 title claims description 177
- 239000004332 silver Substances 0.000 title claims description 177
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 238000004458 analytical method Methods 0.000 claims description 37
- 238000000634 powder X-ray diffraction Methods 0.000 claims description 28
- 238000009616 inductively coupled plasma Methods 0.000 claims description 23
- 239000011701 zinc Substances 0.000 claims description 21
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 20
- 229910052782 aluminium Inorganic materials 0.000 claims description 20
- 229910052797 bismuth Inorganic materials 0.000 claims description 20
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 20
- 229910052725 zinc Inorganic materials 0.000 claims description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 19
- 239000011247 coating layer Substances 0.000 claims description 19
- 229910052710 silicon Inorganic materials 0.000 claims description 19
- 239000010703 silicon Substances 0.000 claims description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 18
- 229910052744 lithium Inorganic materials 0.000 claims description 18
- 239000010410 layer Substances 0.000 claims description 13
- 239000003638 chemical reducing agent Substances 0.000 claims description 12
- 230000000052 comparative effect Effects 0.000 description 43
- 239000002245 particle Substances 0.000 description 38
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 31
- 238000000034 method Methods 0.000 description 22
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 16
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 11
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- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 8
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- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
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- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
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- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
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- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 4
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- 239000012279 sodium borohydride Substances 0.000 description 4
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 229910018068 Li 2 O Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
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Description
本発明は、太陽電池などの半導体電極用の導電性ペーストに含まれる材料として適した銀被覆鉛テルルガラス粉およびその製造方法、ならびに導電性ペーストに関する。 The present invention relates to silver-coated lead tellurium glass powder suitable as a material contained in a conductive paste for a semiconductor electrode such as a solar cell, a method for producing the same, and a conductive paste.
従来より、銀粉、バインダー、溶剤、ガラスフリットなどを含有する導電性ペーストが太陽電池などの半導体電極用に使用されている。
太陽電池などの半導体の電極用途として、ガラスフリットとして酸化テルルを含む鉛テルルガラスを用いることよって、接触抵抗を下げて良好な太陽電池特性が得られる導電性ペーストが提案されている（例えば、特許文献１参照）。
また、鉛テルルガラスを用いた厚膜ペーストを太陽電池の電極に用いることにより反射防止コーティングを貫通し、半導体基板との良い電気的接触を得ることが提案されている（例えば、特許文献２参照）。
Conventionally, conductive pastes containing silver powder, binders, solvents, glass frits and the like have been used for semiconductor electrodes such as solar cells.
As an electrode application for semiconductors such as solar cells, a conductive paste has been proposed in which lead tellur glass containing tellur oxide is used as a glass frit to reduce contact resistance and obtain good solar cell characteristics (for example, patent). Reference 1).
Further, it has been proposed to use a thick film paste using lead tellur glass as an electrode of a solar cell to penetrate an antireflection coating and obtain good electrical contact with a semiconductor substrate (see, for example, Patent Document 2). ).
太陽電池の電極用途として、ペースト作製時のペースト粘度を低減させ、接触抵抗を下げて良好な太陽電池特性が得られる太陽電池電極用のペースト材料および導電性ペーストが求められている。 As a solar cell electrode application, there is a demand for a paste material and a conductive paste for a solar cell electrode, which can reduce the paste viscosity at the time of producing a paste, reduce the contact resistance, and obtain good solar cell characteristics.
本発明は、従来における前記諸問題を解決し、以下の目的を達成することを課題とする。即ち、本発明は、太陽電池の電極用途に用いた場合に、太陽電池の発電効率（以降、変換効率ともいう）を向上させることが可能な銀被覆鉛テルルガラス粉およびその製造方法、ならびに前記銀被覆鉛テルルガラス粉を含有する導電性ペーストを提供することを目的とする。 An object of the present invention is to solve the above-mentioned problems in the past and to achieve the following object. That is, the present invention comprises silver-coated lead tellurium glass powder capable of improving the power generation efficiency (hereinafter, also referred to as conversion efficiency) of the solar cell when used for the electrode application of the solar cell, a method for producing the same, and the above-mentioned. It is an object of the present invention to provide a conductive paste containing silver-coated lead tellurium glass powder.
従来、酸やアルカリに溶けやすいテルルを含む鉛テルルガラス粉については、銀被覆処理が可能であるか予測できず、溶け出す恐れのある鉛テルルガラス粉に対しては銀被覆処理を行う動機が無かった。
そこで、本発明者らが前記鉛テルルガラス粉を用いて銀被覆を試みたところ、銀層による鉛テルルガラス粉の銀被覆はできないことがわかった。しかし、特定の粉末Ｘ線回折ピークを有する鉛テルルガラス粉に銀被覆することができ、得られた銀被覆鉛テルルガラス粉を評価したところ、太陽電池の発電効率を向上させる効果があることを知見した。
Conventionally, it is unpredictable whether lead tellurium glass powder containing tellurium, which is easily dissolved in acid or alkali, can be silver-coated, and there is a motive for silver-coating lead tellurium glass powder, which may dissolve. There wasn't.
Therefore, when the present inventors attempted to coat the lead tellur glass powder with silver using the lead tellur glass powder, it was found that the silver layer could not coat the lead tellur glass powder with silver. However, it is possible to coat the lead tellurium glass powder having a specific powder X-ray diffraction peak with silver, and when the obtained silver-coated lead tellurium glass powder is evaluated, it is found that it has an effect of improving the power generation efficiency of the solar cell. I found out.
本発明者らは、前記目的を解決すべく、鋭意検討した結果、鉛、およびテルルを含み、さらに、リチウム、亜鉛、シリコン、アルミニウム、およびビスマスから選ばれる２つ以上を含む鉛テルルガラス粉の表面に、銀被覆層を有する銀被覆鉛テルルガラス粉であって、前記鉛テルルガラス粉が、粉末Ｘ線回折において、リチウム、亜鉛、シリコン、およびアルミニウムから選ばれる２つ以上またはビスマスを含む酸化物のピークが検出され、鉛を含む酸化物のピークが検出されない銀被覆鉛テルルガラス粉が、太陽電池の電極用途として、ペースト作製時のペースト粘度を低減させ、接触抵抗を下げて良好な太陽電池特性が得られることを見出し、本発明の完成に至った。 As a result of diligent studies to solve the above object, the present inventors have made a lead tellurium glass powder containing lead and tellurium, and further containing two or more selected from lithium, zinc, silicon, aluminum, and bismuth. A silver-coated lead tellurium glass powder having a silver-coated layer on its surface, wherein the lead tellurium glass powder contains two or more selected from lithium, zinc, silicon, and aluminum or bismuth in powder X-ray diffraction. Silver-coated lead tellurium glass powder, in which peaks of substances are detected and peaks of oxides containing lead are not detected, reduces paste viscosity during paste preparation and lowers contact resistance for solar cell electrode applications. We have found that battery characteristics can be obtained, and have completed the present invention.
本発明は、本発明者らによる前記知見に基づくものであり、前記課題を解決するための手段としては、以下の通りである。すなわち、
＜１＞ 鉛、およびテルルを含み、さらに、リチウム、亜鉛、シリコン、アルミニウム、およびビスマスから選ばれる２つ以上を含む鉛テルルガラス粉の表面に、銀被覆層を有する銀被覆鉛テルルガラス粉であって、
前記鉛テルルガラス粉は、粉末Ｘ線回折において、リチウム、亜鉛、シリコン、およびアルミニウムから選ばれる２つ以上を含む酸化物のピークまたはビスマスを含む酸化物のピークが検出され、鉛を含む酸化物のピークが検出されないことを特徴とする銀被覆鉛テルルガラス粉である。
＜２＞ 前記鉛テルルガラス粉が、高周波誘導結合プラズマ（ＩＣＰ）分析値として、テルルを１５質量％〜４０質量％、鉛を１５質量％〜４０質量％含有することを特徴とする前記＜１＞に記載の銀被覆鉛テルルガラス粉である。
＜３＞ 前記銀被覆層が、テルルを含むことを特徴とする前記＜１＞または＜２＞に記載の銀被覆鉛テルルガラス粉である。
＜４＞ 前記＜１＞から＜３＞のいずれかに記載の銀被覆鉛テルルガラス粉を含有することを特徴とする導電性ペーストである。
＜５＞ 太陽電池の電極用であることを特徴とする前記＜４＞に記載の導電性ペーストである。
＜６＞ 鉛、テルルを含み、さらに、リチウム、亜鉛、シリコン、アルミニウム、ビスマスから選ばれる２つ以上を含み、粉末Ｘ線回折において、リチウム、亜鉛、シリコン、およびアルミニウムから選ばれる２つ以上を含む酸化物のピークまたはビスマスを含む酸化物のピークが検出され、鉛を含む酸化物のピークが検出されない鉛テルルガラス粉を、銀錯体溶液に添加した後、還元剤を添加して表面に銀被覆層を形成させることを特徴とする銀被覆鉛テルルガラス粉の製造方法である。
The present invention is based on the above-mentioned findings by the present inventors, and the means for solving the above-mentioned problems are as follows. That is,
<1> A silver-coated lead-tellurium glass powder having a silver-coated layer on the surface of a lead-tellurium glass powder containing lead and tellurium and further containing two or more selected from lithium, zinc, silicon, aluminum, and bismuth. There,
In the lead tellurium glass powder, a peak of an oxide containing two or more selected from lithium, zinc, silicon, and aluminum or a peak of an oxide containing bismuth was detected by powder X-ray diffraction, and an oxide containing lead was detected. It is a silver-coated lead tellurium glass powder characterized in that no peak is detected.
<2> The lead tellurium glass powder contains 15% by mass to 40% by mass of tellurium and 15% by mass to 40% by mass of lead as high frequency inductively coupled plasma (ICP) analysis values. > The silver-coated lead tellurium glass powder described in.
<3> The silver-coated lead tellurium glass powder according to <1> or <2>, wherein the silver-coated layer contains tellurium.
<4> A conductive paste containing the silver-coated lead tellurium glass powder according to any one of <1> to <3>.
<5> The conductive paste according to <4>, which is used for electrodes of a solar cell.
<6> Contains lead and tellurium, and further contains two or more selected from lithium, zinc, silicon, aluminum, and bismuth, and two or more selected from lithium, zinc, silicon, and aluminum in powder X-ray diffraction. Lead tellurium glass powder, in which a peak of an oxide containing bismuth or a peak of an oxide containing bismuth is detected and a peak of an oxide containing lead is not detected, is added to a silver complex solution, and then a reducing agent is added to silver on the surface. It is a method for producing silver-coated lead tellurium glass powder, which comprises forming a coating layer.
本発明によると、太陽電池の電極用途に用いた場合に、太陽電池の発電効率を向上させることが可能な銀被覆鉛テルルガラス粉およびその製造方法、ならびに前記銀被覆鉛テルルガラス粉を含有する導電性ペーストおよびその製造方法を提供することができる。 According to the present invention, it contains silver-coated lead tellurium glass powder capable of improving the power generation efficiency of the solar cell when used for an electrode application of a solar cell, a method for producing the same, and the silver-coated lead tellurium glass powder. A conductive paste and a method for producing the same can be provided.
（銀被覆鉛テルルガラス粉）
本発明の銀被覆鉛テルルガラス粉は、鉛、およびテルルを含み、さらに、リチウム、亜鉛、シリコン、アルミニウム、およびビスマスから選ばれる２つ以上を含む鉛テルルガラス粉の表面に、銀被覆層を有する。
(Silver-coated lead tellurium glass powder)
The silver-coated lead tellurium glass powder of the present invention contains lead and tellurium, and a silver-coated layer is formed on the surface of the lead tellurium glass powder containing two or more selected from lithium, zinc, silicon, aluminum, and bismuth. Have.
＜鉛テルルガラス粉＞
前記鉛テルルガラス粉は、粉末Ｘ線回折において、リチウム、亜鉛、シリコン、およびアルミニウムから選ばれる２つ以上を含む酸化物のピークまたはビスマスを含む酸化物のピークが検出され、鉛を含む酸化物のピークが検出されないガラス粉である。ガラス粉はガラスフリットともいう。
<Lead tellurium glass powder>
In the lead tellurium glass powder, a peak of an oxide containing two or more selected from lithium, zinc, silicon, and aluminum or a peak of an oxide containing bismuth is detected by powder X-ray diffraction, and an oxide containing lead is detected. It is a glass powder in which the peak of is not detected. Glass powder is also called glass frit.
前記粉末Ｘ線回折の方法としては、ＪＩＳ Ｋ ０１３１のＸ線回折分析通則に従い、ＣｕＫαをＸ線源として分析を行うことができる。市販のＸ線回折装置には解析用のソフトウエアが付属しており、前記ソフトウエアと国際回析データセンター（ＩＣＤＤ）のデータベースを用いてピークデータからの結晶性の物質の同定（以下、定性分析ともいう）を行うことができる。前記定性分析としては、統合粉末Ｘ線解析ソフトウェア（ＰＤＸＬ、リガク株式会社製）を用いて、平滑化処理（平滑化条件は、平滑化パラメーター：１０．０、平滑化点数：１１、Ｘ閾値：１．５０）の後、バックグラウンドの除去（ピーク閾値：１．００、強度閾値：１０．０）、Ｋα２除去（強度比：０．４９７０）を行った上で、２次微分法（σカット値：４．５）による自動ピークサーチによって得られたピークに対し、ＩＣＤＤのデータを使用してピーク位置と強度比を元にハナワルト法を用いて行うことができる。 As the method of powder X-ray diffraction, analysis can be performed using CuKα as an X-ray source in accordance with the general rules of X-ray diffraction analysis of JIS K 0131. Commercially available X-ray diffractometers come with software for analysis, and identification of crystalline substances from peak data using the software and the database of the International Center for Diffraction Data (ICDD) (hereinafter, qualitative). (Also called analysis) can be performed. As the qualitative analysis, an integrated powder X-ray analysis software (PDXL, manufactured by Rigaku Co., Ltd.) is used for smoothing processing (smoothing conditions are smoothing parameter: 10.0, smoothing score: 11, X threshold: After 1.50), background removal (peak threshold: 1.00, intensity threshold: 10.0) and Kα2 removal (intensity ratio: 0.4970) are performed, and then the second-order differential method (σ cut) is performed. For the peak obtained by the automatic peak search according to the value: 4.5), the Hanawald method can be used based on the peak position and the intensity ratio using the ICDD data.
ここで、鉛を含む酸化物のピークが検出されないとは、すなわち、ハナワルト法によってピークが全て同定されたときに、鉛を含む酸化物が同定された物質として選択されていない場合をいう。
なお、テルルは反応性が高いため、前記鉛テルルガラス粉において、ガラスとして含まれる場合と、一部が酸化物として含まれる場合と、いずれの場合もある。
Here, the fact that the peak of the oxide containing lead is not detected means that the oxide containing lead is not selected as the identified substance when all the peaks are identified by the Hanawald method.
Since tellurium has high reactivity, the lead tellurium glass powder may be contained as glass or a part thereof as an oxide.
なお、前記銀被覆鉛テルルガラス粉の状態においても、前記粉末Ｘ線回折を同様に行い、その結果から、銀のピークと前記酸化物のピークと非晶質ガラス部分のプロファイルを測定することができる。後述する実施例１−１の鉛テルルガラス粉の粉末Ｘ線回折のデータを図１に、実施例１−１の銀被覆後の銀被覆鉛テルルガラス粉の粉末Ｘ線回折のデータを図２に示す。銀被覆後（図２）は銀被覆前（図１）対して銀のピークが追加されている以外は、ピーク位置は変わらない。よって、銀被覆鉛テルルガラス粉のピークから銀のピークを除いたものを、鉛テルルガラス粉のピークであると同定することができる。 Even in the state of the silver-coated lead tellurium glass powder, the powder X-ray diffraction can be performed in the same manner, and from the result, the profile of the silver peak, the oxide peak, and the amorphous glass portion can be measured. can. The data of powder X-ray diffraction of lead tellurium glass powder of Example 1-1, which will be described later, is shown in FIG. 1, and the data of powder X-ray diffraction of silver-coated lead tellurium glass powder of Example 1-1 after silver coating is shown in FIG. Shown in. After silver coating (Fig. 2), the peak position does not change except that a silver peak is added to that before silver coating (Fig. 1). Therefore, the peak of the silver-coated lead tellurium glass powder minus the silver peak can be identified as the peak of the lead tellurium glass powder.
前記鉛テルルガラス粉としては、適宜製造したものを使用してもよいし、市販品を使用してもよい。前記鉛テルルガラス粉としては、例えば、各成分を含む酸化物を混合し、７００℃〜１，５００℃の温度範囲で溶融し、冷却し、粉砕することにより製造することができる。
前記粉砕の方法としては、特に制限はなく、目的に応じて乾式、湿式を問わず公知の粉砕方法を適宜選択することができる。前記乾式の粉砕方法としては、例えば、ボールミルやジェットミル等を用いる方法などが挙げられ、粉砕助剤を添加することで粉砕効率を向上させることができる。前記湿式の粉砕方法としては、例えば、ボールミルやビーズミル等で溶剤を用いる方法などが挙げられる。前記溶媒としては、例えば、水やアルコールなどの成分が溶出しない溶媒を適宜選択することができる。
As the lead tellur glass powder, those produced as appropriate may be used, or commercially available products may be used. The lead tellur glass powder can be produced, for example, by mixing an oxide containing each component, melting the lead tellur glass powder in a temperature range of 700 ° C. to 1,500 ° C., cooling the glass powder, and pulverizing the lead tellurium glass powder.
The pulverization method is not particularly limited, and a known pulverization method can be appropriately selected regardless of whether it is a dry type or a wet type, depending on the intended purpose. Examples of the dry crushing method include a method using a ball mill, a jet mill, and the like, and the crushing efficiency can be improved by adding a crushing aid. Examples of the wet pulverization method include a method using a solvent in a ball mill, a bead mill, or the like. As the solvent, for example, a solvent in which components such as water and alcohol do not elute can be appropriately selected.
前記鉛テルルガラス粉は、高周波誘導結合プラズマ（ＩＣＰ）分析値として、テルルを１５質量％〜４０質量％、鉛を１５質量％〜４０質量％含有することが好ましい。前記数値範囲を満たすことにより、太陽電池の高い発電効率を得ることができる導電性ペーストを得ることができる。 The lead tellurium glass powder preferably contains 15% by mass to 40% by mass of tellurium and 15% by mass to 40% by mass of lead as high frequency inductively coupled plasma (ICP) analysis values. By satisfying the above numerical range, it is possible to obtain a conductive paste capable of obtaining high power generation efficiency of the solar cell.
前記鉛テルルガラス粉に含まれる、前記リチウム、亜鉛、シリコン、アルミニウム、およびビスマスは、ＩＣＰ分析値として各々０．１質量％以上であれば「含まれる」と判断する。前記リチウム、亜鉛、シリコン、アルミニウム、およびビスマスの含有量の合計としては、２０質量％以下であることが好ましい。
鉛とテルルが、主に、反射防止膜の浸食、および銀拡散の効果があり、リチウム、亜鉛、シリコン、アルミニウム、およびビスマスは、前記効果以外の副次的効果があると考えられる。前記含有量の合計が２０質量％を超えると、相対的に鉛、テルルの含有量が減るため、前記効果が不十分となることがある。
The lithium, zinc, silicon, aluminum, and bismuth contained in the lead tellurium glass powder are judged to be "contained" if they are each 0.1% by mass or more as an ICP analysis value. The total content of lithium, zinc, silicon, aluminum, and bismuth is preferably 20% by mass or less.
Lead and tellurium are considered to have mainly antireflection film erosion and silver diffusion effects, and lithium, zinc, silicon, aluminum and bismuth are considered to have secondary effects other than the above effects. If the total content exceeds 20% by mass, the content of lead and tellurium is relatively reduced, so that the effect may be insufficient.
前記鉛テルルガラス粉に含まれる鉛、テルル、リチウム、亜鉛、シリコン、アルミニウム、およびビスマス以外の成分としては、例えば、ナトリウム（Ｎａ）、カリウム（Ｋ）、ホウ素（Ｂ）、タングステン（Ｗ）、モリブデン（Ｍｏ）、マンガン（Ｍｎ）、鉄（Ｆｅ）、バナジウム（Ｖ）、リン（Ｐ）、アンチモン（Ｓｂ）、マグネシウム（Ｍｇ）、カルシウム（Ｃａ）、ストロンチウム（Ｓｒ）、バリウム（Ｂａ）、チタン（Ｔｉ）、ジルコニウム（Ｚｒ）、ランタン（Ｌａ）などが挙げられる。前記成分の含有量としては、ＩＣＰ分析値として各々０．１質量％以上であれば「含まれる」と判断する。前記成分の含有量の合計としては、１０質量％以下であることが好ましい。 Examples of components other than lead, tellurium, lithium, zinc, silicon, aluminum, and bismuth contained in the lead tellurium glass powder include sodium (Na), potassium (K), boron (B), and tungsten (W). Molybdenum (Mo), manganese (Mn), iron (Fe), vanadium (V), phosphorus (P), antimony (Sb), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), Examples thereof include titanium (Ti), zirconium (Zr), and lantern (La). As for the content of the components, if each is 0.1% by mass or more as an ICP analysis value, it is judged to be "contained". The total content of the components is preferably 10% by mass or less.
前記ＩＣＰ分析で検出される元素の中で、前記粉末Ｘ線回折において結晶性の物質としてピークでの同定ができない元素（鉛など）は、非晶質のガラスとして存在しているものと予想できる。前記粉末Ｘ線回折の結果としては、リチウム、亜鉛、シリコン、およびアルミニウムから選ばれる２つ以上を含む酸化物のピークまたはビスマスを含む酸化物のピークと、ガラス（非晶質）に特徴的な干渉性散乱強度曲線（ハロー）とが、共存した結果が得られる。 Among the elements detected by the ICP analysis, elements (lead, etc.) that cannot be identified at the peak as crystalline substances in the powder X-ray diffraction can be expected to exist as amorphous glass. .. As a result of the powder X-ray diffraction, a peak of an oxide containing two or more selected from lithium, zinc, silicon, and aluminum, or a peak of an oxide containing bismuth, and a glass (amorphous) are characteristic. The result is that the coherent scattering intensity curve (halo) coexists.
前記鉛テルルガラス粉のＩＣＰ分析の方法としては、例えば、前記鉛テルルガラス粉を完全に溶解させてＩＣＰ分析を行う方法が挙げられる。前記銀被覆鉛テルルガラス粉のＩＣＰ分析の方法も同様に行うことができる。
前記鉛テルルガラス粉のＩＣＰ分析の方法としては、例えば、硝酸を用いて前記鉛テルルガラス粉を加熱溶解し、ろ過して得られたろ液をＩＣＰ分析し、その後、ろ紙上の残渣を硝酸とは異なる酸（例えば、塩酸や硫酸）を用いて加熱溶解してＩＣＰ分析し、それぞれのＩＣＰ分析値を加算する方法が挙げられる。前記ＩＣＰ分析による各検出元素の質量％の値は、合計で１００％にはならない。ガラスが酸化物であるのに対し、ＩＣＰ分析では酸素を定量できないためである。そのため、ＩＣＰによる定量値の合計に対する残部（１００−検出元素の質量％の合計値）を、酸素の含有量（質量％）として扱うものとする。また、ＩＣＰ分析値がそのまま、前記鉛テルルガラス粉または前記銀被覆鉛テルルガラス粉中に含まれる各元素の含有量（質量％）を示す。
Examples of the method for ICP analysis of the lead tellur glass powder include a method in which the lead tellur glass powder is completely dissolved to perform ICP analysis. The method of ICP analysis of the silver-coated lead tellurium glass powder can be performed in the same manner.
As a method for ICP analysis of the lead tellurium glass powder, for example, the lead tellurium glass powder is heated and dissolved with nitric acid, the filtrate obtained by filtration is subjected to ICP analysis, and then the residue on the filter paper is treated with nitric acid. Is a method of heating and dissolving using different acids (for example, hydrochloric acid or sulfuric acid), performing ICP analysis, and adding the respective ICP analysis values. The value of mass% of each detected element by the ICP analysis does not become 100% in total. This is because glass is an oxide, whereas oxygen cannot be quantified by ICP analysis. Therefore, the balance (total value of 100-mass% of detected elements) with respect to the total quantitative value by ICP is treated as the oxygen content (mass%). Moreover, the ICP analysis value shows the content (mass%) of each element contained in the lead tellurium glass powder or the silver-coated lead tellurium glass powder as it is.
前記鉛テルルガラス粉の体積基準の粒度分布としては、特に制限はなく、目的に応じて適宜選択することができるが、得られる銀被覆鉛テルルガラス粉の体積平均粒子径に大きく影響する点から、累積５０％粒子径（Ｄ５０）として、０．１μｍ以上２０μｍ以下が好ましく、０．３μｍ以上１０μｍ以下がより好ましく、１μｍ以上５μｍ以下が特に好ましい。累積５０％粒子径（Ｄ５０）が、０．１μｍ未満であるとペーストの粘度が増大して印刷が困難となる場合があり、２０μｍを超えると微細な配線の形成が困難になる場合がある。
前記鉛テルルガラス粉の粒度分布としては、例えば、レーザー回折式粒度分布測定装置（例えば、日機装株式会社製のマイクロトラック）により測定することができる。
The volume-based particle size distribution of the lead tellurium glass powder is not particularly limited and may be appropriately selected depending on the intended purpose, but it greatly affects the volume average particle size of the obtained silver-coated lead tellurium glass powder. The cumulative 50% particle size (D 50 ) is preferably 0.1 μm or more and 20 μm or less, more preferably 0.3 μm or more and 10 μm or less, and particularly preferably 1 μm or more and 5 μm or less. If the cumulative 50% particle size (D 50 ) is less than 0.1 μm, the viscosity of the paste may increase and printing may become difficult, and if it exceeds 20 μm, it may become difficult to form fine wiring. ..
The particle size distribution of the lead tellurium glass powder can be measured by, for example, a laser diffraction type particle size distribution measuring device (for example, Microtrac manufactured by Nikkiso Co., Ltd.).
＜銀被覆層＞
本発明で銀被覆層とは、前記鉛テルルガラス粉の表面上に形成される銀を主成分とする領域をいう。
前記銀被覆層は、銀以外に、鉛テルルガラス粉中の成分のうち溶出しやすい成分を含有する。前記成分としては、少なくともテルルを含有し、さらに必要に応じてその他の成分を含有する。
前記銀被覆層における、銀の含有量としては、６０質量％以上であることが好ましく、銀とテルルの含有量の合計としては、９０質量％以上であることが好ましい。
<Silver coating layer>
In the present invention, the silver coating layer refers to a region containing silver as a main component formed on the surface of the lead tellur glass powder.
In addition to silver, the silver-coated layer contains components in lead tellurium glass powder that are easily eluted. As the component, at least tellurium is contained, and if necessary, other components are contained.
The silver content in the silver coating layer is preferably 60% by mass or more, and the total content of silver and tellurium is preferably 90% by mass or more.
前記銀被覆層中の銀とテルルなどの成分の含有量は、オージェ分光分析装置を用いて鉛テルルガラス粉表面から粉末中央に向けて深さ方向（深さ：０ｎｍから１０ｎｍまで）に定性的および定量的に分析することにより測定することができる。
前記分析の際、有機物などの最表面の付着物に起因すると考えられる炭素や酸素は、前記銀被覆層の成分からは除外する。
前記銀被覆層中のテルルとしては、オージェ分光分析による定性分析で検出されるのに必要な量以上のテルルが含有されていればよい。
The content of components such as silver and tellurium in the silver coating layer is qualitative in the depth direction (depth: from 0 nm to 10 nm) from the surface of the lead tellurium glass powder toward the center of the powder using an Auger spectrophotometer. And can be measured by quantitative analysis.
At the time of the analysis, carbon and oxygen which are considered to be caused by deposits on the outermost surface such as organic substances are excluded from the components of the silver coating layer.
The tellurium in the silver-coated layer may contain more tellurium than necessary for detection by qualitative analysis by Auger spectroscopic analysis.
前記被覆は、鉛テルルガラス粉表面の全部を被覆しても、一部を被覆してもよく、一部を被覆する場合、その被覆率としては、面積で４０％以上が好ましく、５０％以上がより好ましく、６０％以上がさらに好ましく、全部を被覆することが最も好ましい。前記被覆率は、銀被覆鉛テルルガラス粉を例えば、電子線マイクロアナライザ（ＥＰＭＡ）やオージェマップ分析を行うことにより求めることができる。
被覆層は種々の形態をとることができ、一部を被覆する場合は、例えば、銀を主成分とする粒子が鉛テルルガラス粉表面に点在している形態であってもよい。
The coating may cover the entire surface of the lead tellurium glass powder or a part thereof. When covering a part of the surface, the coverage is preferably 40% or more in terms of area, and 50% or more. Is more preferable, 60% or more is further preferable, and it is most preferable to cover the whole. The coverage can be determined by, for example, performing electron probe microanalyzer (EPMA) or Auger map analysis on the silver-coated lead tellurium glass powder.
The coating layer can take various forms, and when partially covering the coating layer, for example, particles containing silver as a main component may be scattered on the surface of the lead tellur glass powder.
前記銀被覆層の平均厚みとしては、１０ｎｍ未満であると太陽電池セルの変換効率が向上せず、１０ｎｍ以上４００ｎｍ以下が好ましく、２０ｎｍ以上３００ｎｍ以下がより好ましく、２００ｎｍを超えて厚くすることによる効果の向上が少ない点から、２００ｎｍ以下がさらに好ましい。
前記被覆層の平均厚みは、オージェ分光分析装置を用いて銀被覆鉛テルルガラス粉表面から粉末中央に向けて深さ方向分析を行った場合の、銀が主成分となる層の深さによって測定することができる。被覆層と原料の鉛テルルガラス粉からなる深部との境界は、例えば、検出されるＡｇのＩｎｔｅｎｓｉｔｙと酸素のＩｎｔｅｎｓｉｔｙとの強弱関係が逆転する位置とすることができる。
また、被覆層の平均厚み（平均深さ）の値は、ＳｉＯ２に対するエッチングレートを用いて、Ａｒスパッタの時間を厚み（深さ）に換算し、任意の値３点以上を平均することにより求めることができる。
When the average thickness of the silver coating layer is less than 10 nm, the conversion efficiency of the solar cell does not improve, and it is preferably 10 nm or more and 400 nm or less, more preferably 20 nm or more and 300 nm or less, and the effect of increasing the thickness to more than 200 nm. 200 nm or less is more preferable from the viewpoint of little improvement.
The average thickness of the coating layer is measured by the depth of the silver-based layer when the depth direction analysis is performed from the surface of the silver-coated lead tellurium glass powder toward the center of the powder using an Auger spectroscopic analyzer. can do. The boundary between the coating layer and the deep portion made of lead tellurium glass powder as a raw material can be, for example, a position where the strength relationship between the detected Ag intensity and the oxygen intensity is reversed.
Further, the value of the average thickness (average depth) of the coating layer is obtained by converting the Ar sputtering time into the thickness (depth) using the etching rate with respect to SiO 2, and averaging 3 or more arbitrary values. Can be sought.
前記銀被覆層を有することにより、ペースト化した際の溶剤や他の銀粉とのなじみがよく、例えば、ペースト化の際に本発明の銀被覆鉛テルルガラス粉を用いると粘度を低くすることができる。太陽電池のフィンガー電極の細線化に伴い、ガラス粉も微細化していくと考えられるが、一般的にガラス粉を微細化していくと増粘する傾向があるため、印刷可能な粘度にするために溶剤の追添加が必要となり、ペースト中の銀含有量は低下し、電極特性やその形状に悪影響を及ぼすと考えられる。一方、本発明の銀被覆鉛テルルガラス粉では、微細化したことによる増粘の影響を低く抑えられるので、溶剤の追添加量を減らすことができて導電性ペースト中の銀含有量の低下を抑制することにより焼成時の密度を上げ、ラインの抵抗等の電極への悪影響を低減することができる。さらに、銀被覆層の存在によりテルルが拡散しやすくなり、太陽電池においてファイヤースルーによるコンタクト抵抗の低減も可能となる。 By having the silver-coated layer, it has good compatibility with the solvent and other silver powder when it is made into a paste. For example, when the silver-coated lead tellurium glass powder of the present invention is used at the time of making a paste, the viscosity can be lowered. can. It is thought that the glass powder will also become finer as the finger electrodes of the solar cell become finer, but in general, as the glass powder becomes finer, the viscosity tends to increase. It is considered that the additional addition of the powder is required, the silver content in the paste is lowered, and the electrode characteristics and the shape thereof are adversely affected. On the other hand, in the silver-coated lead tellurium glass powder of the present invention, the influence of thickening due to miniaturization can be suppressed to a low level, so that the amount of additional solvent added can be reduced and the silver content in the conductive paste can be reduced. By suppressing it, the density at the time of firing can be increased, and adverse effects on the electrodes such as line resistance can be reduced. Further, the presence of the silver coating layer makes it easier for tellurium to diffuse, and it is possible to reduce the contact resistance due to fire-through in the solar cell.
前記銀被覆鉛テルルガラス粉における銀の含有量としては、特に制限はなく、目的に応じて適宜選択することができるが、銀被覆鉛テルルガラス粉全量に対して、ＩＣＰ分析値として、３質量％以上７０質量％以下が好ましく、５質量％以上５０質量％以下がより好ましく、５質量％以上３０質量％以下がさらに好ましい。 The silver content in the silver-coated lead tellurium glass powder is not particularly limited and may be appropriately selected depending on the intended purpose. However, the total amount of silver-coated lead tellurium glass powder is 3 mass as an ICP analysis value. % Or more and 70% by mass or less is preferable, 5% by mass or more and 50% by mass or less is more preferable, and 5% by mass or more and 30% by mass or less is further preferable.
前記銀被覆鉛テルルガラス粉の体積基準の粒度分布としては、特に制限はなく、目的に応じて適宜選択することができるが、累積５０％粒子径（Ｄ５０）として、０．１μｍ以上２０μｍ以下が好ましく、０．３μｍ以上１０μｍ以下がより好ましく、１μｍ以上５μｍ以下が特に好ましい。累積５０％粒子径（Ｄ５０）が、０．１μｍ未満であるとペーストの粘度が増大して印刷が困難となる場合があり、２０μｍを超えると微細な配線の形成が困難になる場合がある。
前記銀被覆鉛テルルガラス粉の粒度分布としては、例えば、レーザー回折式粒度分布測定装置（例えば、日機装株式会社製のマイクロトラック）により測定することができる。
The volume-based particle size distribution of the silver-coated lead tellurium glass powder is not particularly limited and may be appropriately selected depending on the intended purpose, but the cumulative 50% particle size (D 50 ) is 0.1 μm or more and 20 μm or less. Is preferable, 0.3 μm or more and 10 μm or less is more preferable, and 1 μm or more and 5 μm or less is particularly preferable. If the cumulative 50% particle size (D 50 ) is less than 0.1 μm, the viscosity of the paste may increase and printing may become difficult, and if it exceeds 20 μm, it may become difficult to form fine wiring. ..
The particle size distribution of the silver-coated lead tellurium glass powder can be measured by, for example, a laser diffraction type particle size distribution measuring device (for example, Microtrac manufactured by Nikkiso Co., Ltd.).
前記銀被覆鉛テルルガラス粉のＢＥＴ比表面積としては、特に制限はなく、目的に応じて適宜選択することができるが、０．１ｍ２／ｇ以上７０ｍ２／ｇ以下が好ましく、０．５ｍ２／ｇ以上１０ｍ２／ｇ以下がより好ましい。前記ＢＥＴ比表面積としては、例えば、市販のＢＥＴ比表面積測定装置などを用いて測定することができる。 The BET specific surface area of the silver-coated lead tellurium glass powder is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.1 m 2 / g or more and 70 m 2 / g or less, and 0.5 m 2 More preferably, it is at least / g and 10 m 2 / g or less. The BET specific surface area can be measured using, for example, a commercially available BET specific surface area measuring device or the like.
前記銀被覆鉛テルルガラス粉は、脂肪酸などの有機物からなる表面処理剤によって表面が被覆されていてもよい。なお、前記表面処理剤は、前記銀被覆層の成分には含めない。 The surface of the silver-coated lead tellurium glass powder may be coated with a surface treatment agent composed of an organic substance such as a fatty acid. The surface treatment agent is not included in the components of the silver coating layer.
（銀被覆鉛テルルガラス粉の製造方法）
本発明の銀被覆鉛テルルガラス粉の製造方法は、鉛テルルガラス粉を、銀錯体溶液に添加した後、還元剤を添加し、銀の還元反応により、表面に銀被覆層を形成する。さらに必要に応じて被覆後に、ろ過、洗浄、乾燥、解砕、および分級する工程を含んでいてもよい。
前記鉛テルルガラス粉としては、本発明の銀被覆鉛テルルガラス粉における鉛テルルガラス粉について説明した事項を適宜採用することができる。
(Manufacturing method of silver-coated lead tellurium glass powder)
In the method for producing silver-coated lead tellurium glass powder of the present invention, lead tellurium glass powder is added to a silver complex solution, a reducing agent is added, and a silver-coated layer is formed on the surface by a silver reduction reaction. Further, if necessary, a step of filtering, washing, drying, crushing, and classifying after coating may be included.
As the lead tellur glass powder, the matters described for the lead tellur glass powder in the silver-coated lead tellur glass powder of the present invention can be appropriately adopted.
前記銀被覆鉛テルルガラス粉の製造方法は、鉛テルルガラス粉を、銀錯体溶液に添加した後、還元剤を添加して表面に銀被覆層を形成させる還元工程を含み、さらに必要に応じて、銀錯体溶液の調液工程、銀被覆鉛テルルガラス粉を回収するろ過工程、洗浄工程、乾燥工程、解砕工程、分級工程などを含む。 The method for producing silver-coated lead tellurium glass powder includes a reduction step of adding lead tellurium glass powder to a silver complex solution and then adding a reducing agent to form a silver-coated layer on the surface, if necessary. , Includes a preparation step of a silver complex solution, a filtration step of recovering silver-coated lead tellurium glass powder, a washing step, a drying step, a crushing step, a classification step, and the like.
＜調液工程＞
前記調液工程は、銀錯体溶液を調製する工程である。
前記調液工程としては、例えば、純水が撹拌されている反応槽に、銀化合物を入れて銀含有水溶液を得たのち、銀錯化剤を添加することで銀錯体溶液を得ることができる。
前記銀化合物としては、例えば、硝酸銀、炭酸銀、酢酸銀などが挙げられる。
前記銀錯化剤としては、例えば、アンモニア水、アンモニウム塩、ＥＤＴＡなどのキレート化合物などが挙げられる。
ここで、前記銀錯体溶液の２５℃におけるｐＨは、９〜１３の範囲とすることが好ましい。前記ｐＨは、例えば、２５℃において、ｐＨメーター（装置名：ＰＨメータＨＭ−３０Ｇ、東亜ディーケーケー株式会社製）を用いて測定することができる。
<Liquid preparation process>
The liquid preparation step is a step of preparing a silver complex solution.
In the liquid preparation step, for example, a silver complex solution can be obtained by adding a silver compound to a reaction vessel in which pure water is stirred to obtain a silver-containing aqueous solution, and then adding a silver complexing agent. ..
Examples of the silver compound include silver nitrate, silver carbonate, silver acetate and the like.
Examples of the silver complexing agent include aqueous ammonia, ammonium salts, chelating compounds such as EDTA.
Here, the pH of the silver complex solution at 25 ° C. is preferably in the range of 9 to 13. The pH can be measured, for example, at 25 ° C. using a pH meter (device name: PH meter HM-30G, manufactured by DKK-TOA CORPORATION).
＜還元工程＞
前記還元工程は、鉛テルルガラス粉を、銀錯体溶液に添加した後、還元剤を添加して表面に銀被覆層を形成させる工程である。
前記還元剤としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、アスコルビン酸、亜硫酸塩、アルカノールアミン、過酸化水素水、ギ酸、ギ酸アンモニウム、ギ酸ナトリウム、グリオキサール、酒石酸、次亜燐酸ナトリウム、水素化ホウ素ナトリウム、ヒドロキノン、ヒドラジン、ヒドラジン誘導体、ピロガロール、ぶどう糖、没食子酸、ホルマリン、無水亜硫酸ナトリウム、ロンガリットなどが挙げられる。これらは、１種単独で使用してもよいし、２種以上を併用してもよい。これらの中でも、アスコルビン酸、アルカノールアミン、水素化ホウ素ナトリウム、ヒドロキノン、ヒドラジン、ホルマリンが好ましく、安価な点から、ホルマリン、ヒドラジン、水素化ホウ素ナトリウムがより好ましい。
前記還元剤の添加量としては、特に制限はなく、目的に応じて適宜選択することができる。
<Reduction process>
The reduction step is a step of adding lead tellurium glass powder to a silver complex solution and then adding a reducing agent to form a silver coating layer on the surface.
The reducing agent is not particularly limited and may be appropriately selected depending on the intended purpose. For example, ascorbic acid, sulfite, alkanolamine, hydrogen peroxide solution, formic acid, ammonium formate, sodium formate, glyoxal, tartrate, etc. Examples thereof include sodium hypophosphate, sodium borohydride, hydroquinone, hydrazine, hydrazine derivative, pyrogallol, glucose, formic acid, formic acid, sodium anhydrous sodium sulfite, and longalite. These may be used alone or in combination of two or more. Among these, ascorbic acid, alkanolamine, sodium borohydride, hydroquinone, hydrazine, and formalin are preferable, and formalin, hydrazine, and sodium borohydride are more preferable from the viewpoint of low cost.
The amount of the reducing agent added is not particularly limited and may be appropriately selected depending on the intended purpose.
前記還元剤と併せて、還元助剤を用いてもよい。
前記還元助剤としては、特に制限はなく、目的に応じて適宜選択することができるが、水素化ホウ素ナトリウム、コロイド粒子が好ましい。前記コロイド粒子が分散した液を添加することにより、ナノサイズの粒子が核となり、銀が析出する場を増やすため、未還元銀をなくすことが可能である。前記コロイド粒子としては、導電性の観点から、ナノサイズの金属のコロイド粒子を用いることが好ましく、銀コロイド液が特に好ましい。
A reducing aid may be used in combination with the reducing agent.
The reducing aid is not particularly limited and may be appropriately selected depending on the intended purpose, but sodium borohydride and colloidal particles are preferable. By adding the liquid in which the colloidal particles are dispersed, the nano-sized particles become nuclei and the place where silver is precipitated is increased, so that unreduced silver can be eliminated. As the colloidal particles, it is preferable to use nano-sized metal colloidal particles from the viewpoint of conductivity, and a silver colloidal liquid is particularly preferable.
前記還元剤添加後、銀錯体溶液中の未反応の銀が無くなるまで撹拌を継続することが好ましい。前記還元工程の液温としては、１０℃以上５０℃以下が好ましい。 After adding the reducing agent, it is preferable to continue stirring until the unreacted silver in the silver complex solution disappears. The liquid temperature in the reduction step is preferably 10 ° C. or higher and 50 ° C. or lower.
前記還元剤の添加前、添加後、未反応の銀が無くなった頃、のいずれかにおいて、脂肪酸や界面活性剤などの表面処理剤を添加してもよい。これにより、粉末が凝集することを抑制することができる。 A surface treatment agent such as a fatty acid or a surfactant may be added at any of the time before, after the addition of the reducing agent, and when the unreacted silver disappears. As a result, it is possible to prevent the powder from agglomerating.
＜ろ過工程、洗浄工程、乾燥工程、解砕工程、および分級工程＞
前記分散工程で得られる銀被覆鉛テルルガラス粉含有スラリーを吸引ろ過し、水洗することによって、流動性がほとんどない塊状のケーキが得られる。ケーキの乾燥を早める、乾燥時の凝集を防ぐ、などの目的で、ケーキ中の水を低級アルコールやポリオールなどで置換してもよい。前記ケーキを強制循環式大気乾燥機、真空乾燥機、気流乾燥装置等の乾燥機によって乾燥することにより、銀テルル被覆ガラス粉が得られる。乾燥後または乾燥中に解砕を行ってもよい。粒子を機械的に流動化させることができる装置に銀被覆鉛テルルガラス粉を投入して、粒子同士を機械的に衝突させることによって、銀被覆鉛テルルガラス粉の表面の凹凸や角張った部分を滑らかにする表面平滑化処理を行ってもよい。さらに分級処理を行ってもよい。乾燥、解砕、および分級を行うことができる一体型の装置を用いてもよい。
<Filtration process, cleaning process, drying process, crushing process, and classification process>
The silver-coated lead tellurium glass powder-containing slurry obtained in the dispersion step is suction-filtered and washed with water to obtain a lumpy cake having almost no fluidity. The water in the cake may be replaced with a lower alcohol, a polyol, or the like for the purpose of accelerating the drying of the cake, preventing agglomeration during drying, and the like. Silver tellurium-coated glass powder is obtained by drying the cake with a dryer such as a forced circulation air dryer, a vacuum dryer, or an air flow dryer. Crushing may be carried out after or during drying. By putting silver-coated lead tellurium glass powder into a device that can mechanically fluidize the particles and mechanically colliding the particles with each other, the unevenness and angular parts of the surface of the silver-coated lead tellurium glass powder are removed. A surface smoothing treatment for smoothing may be performed. Further, the classification process may be performed. An integrated device capable of drying, crushing, and classifying may be used.
（導電性ペースト）
本発明の導電性ペーストは、本発明の銀被覆鉛テルルガラス粉を含有し、銀粉等の導電粉、樹脂、および有機溶媒を含有することが好ましく、さらに必要に応じてその他の成分を含有する。なお、前記銀被覆鉛テルルガラス粉以外のガラスフリットをさらに含有していてもよい。
(Conductive paste)
The conductive paste of the present invention contains the silver-coated lead tellurium glass powder of the present invention, preferably contains a conductive powder such as silver powder, a resin, and an organic solvent, and further contains other components as necessary. .. In addition, a glass frit other than the silver-coated lead tellurium glass powder may be further contained.
本発明の銀被覆鉛テルルガラス粉を含有した前記導電性ペーストは、従来の導電性ペーストと比較して、焼成型の太陽電池の電極、種々の電子部品の電極や回路などを形成するための導電性ペーストとして、好適に利用可能である。 The conductive paste containing the silver-coated lead tellurium glass powder of the present invention is used for forming electrodes of a firing-type solar cell, electrodes and circuits of various electronic components, as compared with the conventional conductive paste. It can be suitably used as a conductive paste.
以下、本発明の実施例を説明するが、本発明は、これらの実施例に何ら限定されるものではない。 Hereinafter, examples of the present invention will be described, but the present invention is not limited to these examples.
（実施例１−１）
＜鉛テルルガラス粉の作製＞
酸化物粉として、ＴｅＯ２（３０ｍｏｌ％）、ＰｂＯ（３５ｍｏｌ％）、Ｌｉ２Ｏ３（１５ｍｏｌ％）、ＺｎＯ（１０ｍｏｌ％）、ＳｉＯ２（５ｍｏｌ％）、およびＡｌ２Ｏ３（５ｍｏｌ％）を秤量し、混合して溶融、冷却、粉砕することにより実施例１−１の鉛テルルガラス粉（累積５０％粒子径（Ｄ５０）＝３．８μｍ）１０ｇを得た。
(Example 1-1)
<Making lead tellur glass powder>
TeO 2 (30 mol%), PbO (35 mol%), Li 2 O 3 (15 mol%), Zn O (10 mol%), SiO 2 (5 mol%), and Al 2 O 3 (5 mol%) were used as oxide powders. By weighing, mixing, melting, cooling, and pulverizing, 10 g of lead tellurium glass powder (cumulative 50% particle diameter (D 50 ) = 3.8 μm) of Example 1-1 was obtained.
図１に、実施例１−１の鉛テルルガラス粉の粉末Ｘ線回折による定性分析データを示す。粉末Ｘ線回折は、全自動水平型多目的Ｘ線回折装置（装置名：ＳｍａｒｔＬａｂ、株式会社リガク製）を用い、Ｘ線源をＣｕＫα（電圧４５ｋＶ、電流２００ｍＡ）とし、ステップ：０．０１°、測定範囲：２０°〜８０°、測定速度：６°/分間の条件で測定した。
図１からは結晶性のピークが観察され、統合粉末Ｘ線解析ソフトウェア（ＰＤＸＬ、リガク株式会社製）を用いて、平滑化処理（平滑化条件は、平滑化パラメーター：１０．０、平滑化点数：１１、Ｘ閾値：１．５０）の後、バックグラウンドの除去（ピーク閾値：１．００、強度閾値：１０．０）、Ｋα２除去（強度比：０．４９７０）を行った上で、２次微分法（σカット値：４．５）による自動ピークサーチを行った。
FIG. 1 shows qualitative analysis data of lead tellurium glass powder of Example 1-1 by powder X-ray diffraction. For powder X-ray diffraction, a fully automatic horizontal multipurpose X-ray diffractometer (device name: SmartLab, manufactured by Rigaku Co., Ltd.) is used, the X-ray source is CuKα (voltage 45 kV, current 200 mA), and the step: 0.01 °, The measurement was performed under the conditions of measurement range: 20 ° to 80 ° and measurement speed: 6 ° / min.
A crystallinity peak was observed from FIG. 1, and a smoothing process (smoothing conditions were smoothing parameter: 10.0, smoothing score) was performed using integrated powder X-ray analysis software (PDXL, manufactured by Rigaku Co., Ltd.). : 11, X threshold: 1.50), background removal (peak threshold: 1.00, intensity threshold: 10.0), Kα2 removal (intensity ratio: 0.4970), and then 2 An automatic peak search was performed by the next differential method (σ cut value: 4.5).
自動ピークサーチによって得られた各ピークは、定性分析によって、亜鉛−アルミニウムの複合酸化物（ＺｎＡｌ２Ｏ４）、リチウム−アルミニウム−ケイ素複合酸化物（ＬｉＡｌＳｉＯ４）、酸化ケイ素（ＳｉＯ２）によるものと同定された。鉛を含む酸化物によるピークは検出されなかった。すなわち、鉛テルルガラス粉は、リチウム、亜鉛、シリコン、およびアルミニウムから選ばれる２つ以上を含む結晶性を有する酸化物と、鉛を含む非晶質のガラスとを含むことが分かる。 Each peak obtained by the automatic peak search is due to zinc-aluminum composite oxide (ZnAl 2 O 4 ), lithium-aluminum-silicon composite oxide (LiAlSiO 4 ), and silicon oxide (SiO 2 ) by qualitative analysis. Was identified. No peaks due to lead-containing oxides were detected. That is, it can be seen that the lead tellurium glass powder contains a crystalline oxide containing two or more selected from lithium, zinc, silicon, and aluminum, and an amorphous glass containing lead.
＜銀被覆鉛テルルガラス粉の作製＞
銀３２質量％の硝酸銀水溶液３．４７ｇを純水７８７ｇが撹拌されている状態の１Ｌビーカーに混合して希釈し、銀を１．１１ｇ含む硝酸銀水溶液とした。引き続き、このビーカー中へ錯体化剤としての２８質量％のアンモニア水２．５ｇを添加し、銀アンミン錯塩水溶液を得た（２５℃におけるｐＨ：１１）。
<Preparation of silver-coated lead tellurium glass powder>
3.47 g of a 32 mass% silver nitrate aqueous solution was mixed with a 1 L beaker in which 787 g of pure water was stirred and diluted to obtain a silver nitrate aqueous solution containing 1.11 g of silver. Subsequently, 2.5 g of 28% by mass ammonia water as a compositing agent was added to this beaker to obtain an aqueous silver-ammine complex salt solution (pH: 11 at 25 ° C.).
この銀アンミン錯塩水溶液の液温を３０℃とした後、実施例１−１の鉛テルルガラス粉を１０ｇ投入し、その直後に、還元剤としてのヒドラジン０．３ｇ、銀コロイド［溶媒：純水、含有するナノ粒子銀のＴＥＭ粒径：５ｎｍ〜４０ｎｍ、ナノ粒子銀の含有量：０．０１ｇ（水溶液中の銀量に対して０．００１倍）］１０．３ｇ、および純水２０ｇを予め混合したものを投入し、熟成時間（未還元銀が液中に残らないようにする待ち時間）を５分間として、銀を主成分とする被覆層を鉛テルルガラス粉表面に形成させた。前記吸引ろ過時のろ液の２５℃におけるｐＨは９．６であり、ろ液についてＩＣＰ発光分析（ＳＰＳ５１００、ＳＩＩ社製）したところ、テルルの含有量が８１ｐｐｍであった。鉛テルルガラス粉中のテルルは溶出しやすい成分であり、銀被覆層中にも含有されることが推測される。 After the liquid temperature of this silver ammine complex salt aqueous solution was set to 30 ° C., 10 g of the lead tellurium glass powder of Example 1-1 was added, and immediately after that, 0.3 g of hydrazine as a reducing agent and silver colloid [solvent: pure water] were added. , TEM particle size of nanoparticle silver contained: 5 nm to 40 nm, content of nanoparticle silver: 0.01 g (0.001 times the amount of silver in an aqueous solution)] 10.3 g, and 20 g of pure water in advance. The mixture was added, and the aging time (waiting time for preventing unreduced silver from remaining in the liquid) was set to 5 minutes, and a coating layer containing silver as a main component was formed on the surface of lead tellurium glass powder. The pH of the filtrate at 25 ° C. during suction filtration was 9.6, and when the filtrate was subjected to ICP emission analysis (SPS5100, manufactured by SII), the tellurium content was 81 ppm. Tellurium in lead tellurium glass powder is a component that easily elutes, and it is presumed that it is also contained in the silver coating layer.
還元剤投入から５分間後に、銀被覆ガラス粉含有スラリーを吸引濾過し、純水を用いて洗浄後液の電位が０．５ｍＳ／ｍ以下となるまで水洗して、ケーキを得た。得られたケーキを７５℃の真空乾燥機で１０時間乾燥させ、実施例１−１の銀被覆鉛テルルガラス粉を得た。
図２に、実施例１−１の銀被覆鉛テルルガラス粉の粉末Ｘ線回折によるＸ線分析データを示す。図２中、＊は、銀（Ａｇ）を示す。
After 5 minutes from the addition of the reducing agent, the silver-coated glass powder-containing slurry was suction-filtered, washed with pure water until the potential of the liquid became 0.5 mS / m or less, and a cake was obtained. The obtained cake was dried in a vacuum dryer at 75 ° C. for 10 hours to obtain the silver-coated lead tellurium glass powder of Example 1-1.
FIG. 2 shows X-ray analysis data by powder X-ray diffraction of the silver-coated lead tellurium glass powder of Example 1-1. In FIG. 2, * indicates silver (Ag).
図２と、銀被覆前の鉛テルルガラス粉のＸ線分析結果である図１とを比較すると、銀（Ａｇ）のピークがある以外はピーク位置が同じであり、内部の鉛テルルガラス粉を構成する組成に変化が無いことが分かる。したがって、銀被覆鉛テルルガラス粉の粉末Ｘ線回折によっても、銀被覆前の鉛テルルガラス粉の粉末Ｘ線回折と同様に、酸化物のピークの検出の有無を評価できることが分かる。
得られた銀被覆鉛テルルガラス粉について、さらに以下の分析を行った。
Comparing FIG. 2 with FIG. 1, which is the result of X-ray analysis of lead tellurium glass powder before silver coating, the peak positions are the same except that there is a silver (Ag) peak, and the lead tellurium glass powder inside is used. It can be seen that there is no change in the constituent composition. Therefore, it can be seen that the presence or absence of the detection of the oxide peak can be evaluated by the powder X-ray diffraction of the silver-coated lead tellurium glass powder as well as the powder X-ray diffraction of the lead tellurium glass powder before the silver coating.
The following analysis was further performed on the obtained silver-coated lead tellurium glass powder.
［オージェ分光分析］
オージェ分光分析装置（ＪＡＭＰ−９５００Ｆ、日本電子株式会社製）により銀被覆鉛テルルガラスの最表面の定性分析を行うと、銀以外にテルルおよび亜鉛のピークが観察された。鉛テルルガラスからのテルルの一部溶解によって銀被覆層には銀以外にテルルおよび亜鉛が含まれていることが分かる。
また、深さ方向の定量分析を行うと、最表面（深さ０ｎｍから１０ｎｍまで）におけるＡｇは７８質量％、Ｔｅは１２質量％、Ｚｎは４質量％であった。
[Auger spectroscopic analysis]
When the outermost surface of the silver-coated lead tellurium glass was qualitatively analyzed by an Auger spectrophotometer (JAMP-9500F, manufactured by JEOL Ltd.), peaks of tellurium and zinc were observed in addition to silver. Partial dissolution of tellurium from lead tellurium glass reveals that the silver coating layer contains tellurium and zinc in addition to silver.
Further, when the quantitative analysis in the depth direction was performed, Ag was 78% by mass, Te was 12% by mass, and Zn was 4% by mass on the outermost surface (depth from 0 nm to 10 nm).
[ＩＣＰ分析による組成分析]
鉛テルルガラスについて試料０．０４ｇ〜０．０５ｇを硝酸（精密分析用試薬（ＵＧＲ）、６０質量％〜６１質量％、関東化学株式会社）５ｍＬと蒸留水１０ｍＬ以下とを用いて加熱溶解し、放冷した後、ろ紙（Ｎｏ．５Ｃ、ＡＤＶＡＮＴＥＣ社製）を通過させ、ろ液を５０ｍＬ定容し、ＩＣＰ（ＳＰＳ５１００、ＳＩＩ社製）により第１の測定を行った。
ろ紙上の残渣を蒸留水で石英ビーカーに移し、塩酸（精密分析用試薬（ＵＧＲ）、３５質量％〜３７質量％、関東化学株式会社）５ｍＬと、硫酸（精密分析用試薬（ＵＧＲ）、９６質量％、関東化学株式会社）２ｍＬを入れて加熱溶解すると硫酸白煙を発して乾固した。次に、純水１０ｍＬ以下と塩酸５ｍＬとを添加して加熱溶解し、放冷後５０ｍＬ定容し、ＩＣＰで第２の測定を行った。
第１の測定および第２の測定の測定値を合計して、銀被覆鉛テルルガラスに含まれる元素の定性と定量を行った。結果を表１に示す。鉛テルルガラス粉に含まれる元素の定性と定量についても同様にして行うことができる。
[Composition analysis by ICP analysis]
For lead tellurium glass, 0.04 g to 0.05 g of a sample was heated and dissolved using 5 mL of nitrate (reagent for precision analysis (UGR), 60% by mass to 61% by mass, Kanto Chemical Co., Inc.) and 10 mL or less of distilled water. After allowing to cool, the mixture was passed through a filter paper (No. 5C, manufactured by ADVANTEC), 50 mL of the filtrate was constant volume, and the first measurement was performed by ICP (SPS5100, manufactured by SII).
The residue on the filter paper is transferred to a quartz beaker with distilled water, and 5 mL of hydrochloric acid (reagent for precision analysis (UGR), 35% by mass to 37% by mass, Kanto Chemical Co., Inc.) and sulfuric acid (reagent for precision analysis (UGR), 96). (% by mass, Kanto Chemical Co., Inc.) When 2 mL was added and dissolved by heating, white sulfuric acid smoke was emitted and dried. Next, 10 mL or less of pure water and 5 mL of hydrochloric acid were added and dissolved by heating, and after allowing to cool, the volume was adjusted to 50 mL, and the second measurement was carried out by ICP.
The measured values of the first measurement and the second measurement were summed to perform qualitative analysis and quantification of the elements contained in the silver-coated lead tellurium glass. The results are shown in Table 1. The same can be done for the qualitative analysis and quantification of the elements contained in the lead tellurium glass powder.
［粒度分布］
銀被覆鉛テルルガラス粉の体積基準の粒度分布としては、銀被覆鉛テルルガラス粉１ｇを２−プロパノール（一級２−プロパノール、和光純薬工業株式会社製）４０ｍＬ中で超音波ホモジナイザー（超音波ＵＳ−１５０Ｔ、株式会社日本精機製作所製、チップ：直径２０ｍｍ、ＡＵＴＰＵＴ ＡＤＪ９、Ｖ−ＬＥＶＥＬ：３００μＡ〜３５０μＡで分散させ、レーザー回折式粒度分布装置（株式会社日機装株式会社製のマイクロトラック粒度分布測定装置（ＭＴ３３００ＥＸＩＩ、Ｍｉｃｒｏｔｒａｃ社製））により測定して、累積１０％粒子径（Ｄ１０）、累積５０％粒子径（Ｄ５０）、および累積９０％粒子径（Ｄ９０）を求めた。結果を表１に示した。
[Particle size distribution]
As a volume-based particle size distribution of silver-coated lead tellurium glass powder, an ultrasonic homogenizer (ultrasonic US) in 40 mL of 2-propanol (first-class 2-propanol, manufactured by Wako Pure Chemical Industries, Ltd.) containing 1 g of silver-coated lead tellurium glass powder. -150T, manufactured by Nippon Seiki Seisakusho Co., Ltd., chip:
（比較例１−１）
実施例１−１で使用した鉛テルルガラス粉をそのまま用い、銀被覆しなかったこと以外は、実施例１と同様にして比較例１−１の鉛テルルガラス粉を得た。実施例１−１と同様にして、粒度分布および組成分析を行った。結果を表１に示した。
(Comparative Example 1-1)
The lead tellurium glass powder used in Example 1-1 was used as it was, and the lead tellurium glass powder of Comparative Example 1-1 was obtained in the same manner as in Example 1 except that it was not coated with silver. Particle size distribution and composition analysis were performed in the same manner as in Example 1-1. The results are shown in Table 1.
（実施例２−１）
実施例１−１の鉛テルルガラス粉を乾式ボールミル（装置名：ボールミル架台、伊藤製作所製、メディアの材質：Ａｌ２Ｏ３、直径：１０ｍｍと２０ｍｍの混合）により粉砕し、累積５０％粒子径（Ｄ５０）を３．８μｍから１．５μｍまで小さくして実施例２−１の鉛テルルガラス粉を得、これを使用したこと以外は、実施例１−１と同様にして実施例２−１の銀被覆鉛テルルガラス粉を得た。実施例１−１と同様にして、粒度分布および組成分析を行った。結果を表１に示した。
(Example 2-1)
The lead tellurium glass powder of Example 1-1 was pulverized by a dry ball mill (device name: ball mill mount, manufactured by Ito Seisakusho, media material: Al 2 O 3 , diameter: a mixture of 10 mm and 20 mm), and a cumulative 50% particle diameter. (D 50 ) was reduced from 3.8 μm to 1.5 μm to obtain the lead tellurium glass powder of Example 2-1. Except for the fact that this was used, Example 2-in the same manner as in Example 1-1. 1 silver-coated lead tellurium glass powder was obtained. Particle size distribution and composition analysis were performed in the same manner as in Example 1-1. The results are shown in Table 1.
（比較例２−１）
実施例２−１の鉛テルルガラス粉をそのまま用い、銀被覆しなかったこと以外は、実施例２−１と同様にして比較例２−１の鉛テルルガラス粉を得た。実施例１−１と同様にして、粒度分布および組成分析を行った。結果を表１に示した。
(Comparative Example 2-1)
The lead tellurium glass powder of Example 2-1 was used as it was, and the lead tellurium glass powder of Comparative Example 2-1 was obtained in the same manner as in Example 2-1 except that it was not coated with silver. Particle size distribution and composition analysis were performed in the same manner as in Example 1-1. The results are shown in Table 1.
（実施例３−１）
酸化物粉として、ＴｅＯ２（２４ｍｏｌ％）、ＰｂＯ（４１．５ｍｏｌ％）、Ｂｉ２Ｏ３（７．５ｍｏｌ％）、ＳｉＯ２（９ｍｏｌ％）、Ｌｉ２Ｏ３（８ｍｏｌ％）、ＺｎＯ（６ｍｏｌ％）、ＷＯ３（３ｍｏｌ％）、およびＳｂ２Ｏ３（１ｍｏｌ％）を秤量し、混合して溶融、冷却、粉砕することにより実施例３−１の鉛テルルガラス粉（累積５０％粒子径（Ｄ５０）＝３．８μｍ）１０ｇを得た。
(Example 3-1)
As oxide powder, TeO 2 (24 mol%), PbO (41.5 mol%), Bi 2 O 3 (7.5 mol%), SiO 2 (9 mol%), Li 2 O 3 (8 mol%), ZnO (6 mol%) %), WO 3 (3 mol%), and Sb 2 O 3 (1 mol%) are weighed, mixed, melted, cooled, and pulverized to obtain lead tellurium glass powder of Example 3-1 (cumulative 50% particle size). (D 50 ) = 3.8 μm) 10 g was obtained.
実施例１−１と同様にして測定した、実施例３−１の鉛テルルガラス粉の粉末Ｘ線回析によるＸ線分析データを図３に示す。
自動ピークサーチによって得られた各ピーク（図３中、◆で示す。）は、定性分析によって、ビスマス−テルルの複合酸化物（Ｂｉ３．２Ｔｅ０．８Ｏ６．４）であると同定された。鉛を含む酸化物によるピークは検出されなかった。すなわち、ビスマスを含む結晶性を有する酸化物と、鉛を含む非晶質のガラスとを含むことが分かる。なお、表１の実施例３−１の鉛テルルガラス粉（比較例３−１）のＩＣＰ分析値より、全てのビスマスが複合酸化物となっていた場合でもテルルは大半が非晶質のガラスとして存在していることは明らかである。
FIG. 3 shows X-ray analysis data obtained by powder X-ray diffraction of lead tellurium glass powder of Example 3-1 measured in the same manner as in Example 1-1.
Each peak obtained by the automatic peak search (indicated by ◆ in FIG. 3) was identified by qualitative analysis as a bismuth-tellurium composite oxide (Bi 3.2 Te 0.8 O 6.4 ). Was done. No peaks due to lead-containing oxides were detected. That is, it can be seen that it contains a crystalline oxide containing bismuth and an amorphous glass containing lead. From the ICP analysis values of the lead tellurium glass powder (Comparative Example 3-1) of Example 3-1 in Table 1, most of the tellurium is amorphous glass even when all the bismuths are composite oxides. It is clear that it exists as.
次いで、実施例１−１において、実施例１−１の鉛テルルガラス粉に代えて、実施例３−１の鉛テルルガラス粉を用いたこと以外は、実施例１−１と同様にして実施例３−１の銀被覆鉛テルルガラス粉を得た。実施例１−１と同様にして、粒度分布および組成分析を行った。結果を表１に示した。 Next, in Example 1-1, the same procedure as in Example 1-1 was carried out except that the lead tellur glass powder of Example 3-1 was used instead of the lead tellur glass powder of Example 1-1. The silver-coated lead tellurium glass powder of Example 3-1 was obtained. Particle size distribution and composition analysis were performed in the same manner as in Example 1-1. The results are shown in Table 1.
実施例３−１の銀被覆鉛テルルガラス粉の粉末Ｘ線回折によるＸ線分析データを図４に示す。図４中、◆は、ビスマス−テルルの複合酸化物（Ｂｉ３．２Ｔｅ０．８Ｏ６．４）を示し、＊は、銀（Ａｇ）を示す。
図４と、銀被覆前の鉛テルルガラス粉のＸ線分析結果である図３とを比較すると、銀（Ａｇ）のピークがある以外はピーク位置が同じであり、内部の鉛テルルガラス粉を構成する組成に変化が無いことが分かる。
The X-ray analysis data by the powder X-ray diffraction of the silver-coated lead tellurium glass powder of Example 3-1 is shown in FIG. In FIG. 4, ◆ indicates a bismuth-tellurium composite oxide (Bi 3.2 Te 0.8 O 6.4 ), and * indicates silver (Ag).
Comparing FIG. 4 with FIG. 3, which is the result of X-ray analysis of lead tellurium glass powder before silver coating, the peak positions are the same except that there is a silver (Ag) peak, and the lead tellurium glass powder inside is used. It can be seen that there is no change in the constituent composition.
（比較例３−１）
実施例３−１の鉛テルルガラス粉をそのまま用い、銀被覆しなかったこと以外は、実施例３−１と同様にして比較例３−１の鉛テルルガラス粉を得た。実施例１−１と同様にして、粒度分布および組成分析を行った。結果を表１に示した。
(Comparative Example 3-1)
The lead tellurium glass powder of Example 3-1 was used as it was, and the lead tellurium glass powder of Comparative Example 3-1 was obtained in the same manner as in Example 3-1 except that it was not coated with silver. Particle size distribution and composition analysis were performed in the same manner as in Example 1-1. The results are shown in Table 1.
（比較例４−１）
酸化物粉として、ＴｅＯ２（４０ｍｏｌ％）、ＰｂＯ（２５ｍｏｌ％）、Ｌｉ２Ｏ３（１５ｍｏｌ％）、ＺｎＯ（１０ｍｏｌ％）、ＳｉＯ２（５ｍｏｌ％）、およびＡｌ２Ｏ３（５ｍｏｌ％）を秤量し、混合して溶融、冷却、粉砕することにより比較例４−１の鉛テルルガラス粉（累積５０％粒子径（Ｄ５０）＝３．３μｍ）１０ｇを得た。鉛テルルガラス粉をそのまま用い、銀被覆しなかった。実施例１−１と同様にして、粒度分布および組成分析を行った。結果を表１に示した。
(Comparative Example 4-1)
TeO 2 (40 mol%), PbO (25 mol%), Li 2 O 3 (15 mol%), Zn O (10 mol%), SiO 2 (5 mol%), and Al 2 O 3 (5 mol%) were used as oxide powders. By weighing, mixing, melting, cooling, and pulverizing, 10 g of lead tellurium glass powder (cumulative 50% particle diameter (D 50 ) = 3.3 μm) of Comparative Example 4-1 was obtained. Lead tellurium glass powder was used as it was and was not silver-coated. Particle size distribution and composition analysis were performed in the same manner as in Example 1-1. The results are shown in Table 1.
実施例１−１と同様にして測定した、比較例４−１の鉛テルルガラス粉の粉末Ｘ線回析によるＸ線分析データを図５に示した。
自動ピークサーチによって得られた各ピークは、定性分析によって、亜鉛−アルミニウムの複合酸化物（ＺｎＡｌ２Ｏ４）、リチウム−アルミニウム−ケイ素複合酸化物（ＬｉＡｌＳｉＯ４）、酸化ケイ素（ＳｉＯ２）によるものと同定された。鉛を含む酸化物によるピークは検出されなかった。
また、実施例１−１の図１と比較し、強度比は異なるものの、同じピーク位置（組成）であった。
The X-ray analysis data by the powder X-ray diffraction of the lead tellurium glass powder of Comparative Example 4-1 measured in the same manner as in Example 1-1 is shown in FIG.
Each peak obtained by the automatic peak search is due to zinc-aluminum composite oxide (ZnAl 2 O 4 ), lithium-aluminum-silicon composite oxide (LiAlSiO 4 ), and silicon oxide (SiO 2 ) by qualitative analysis. Was identified. No peaks due to lead-containing oxides were detected.
Further, as compared with FIG. 1 of Example 1-1, although the intensity ratio was different, the peak position (composition) was the same.
（比較例５−１）
実施例２−１の鉛テルルガラス粉（累積５０％粒子径（Ｄ５０）＝１．６μｍ）を、３５０℃１時間熱処理を行って比較例５の鉛テルルガラス粉を得た後、実施例２−１と同様に銀被覆を行って比較例５−１の銀被覆鉛テルルガラス粉を得た。
実施例１−１と同様にして測定した、比較例５−１の鉛テルルガラス粉の粉末Ｘ線回析によるＸ線分析データを図６に示した。
熱処理後の比較例５の鉛テルルガラス粉のＸ線回折結果を見ると、結晶性のピークが多く観察された。自動ピークサーチによって得られた各ピークは、定性分析によって、ＰｂＴｅＯ３、ＺｎＡｌ２Ｏ４、Ｐｂ２Ｔｅ３Ｏ８、ＳｉＯ２（α−ＳｉＯ２）、Ｌｉ２Ａｌ２Ｓｉ３Ｏ１０、ＬｉＡｌ２Ｏ４、およびＳｉＯ２によるものと同定された。したがって、鉛を含む酸化物によるピークが検出された。
(Comparative Example 5-1)
The lead tellur glass powder of Example 2-1 (cumulative 50% particle diameter (D 50 ) = 1.6 μm) was heat-treated at 350 ° C. for 1 hour to obtain the lead tellur glass powder of Comparative Example 5, and then Examples. Silver coating was performed in the same manner as in 2-1 to obtain silver-coated lead tellurium glass powder of Comparative Example 5-1.
FIG. 6 shows X-ray analysis data obtained by powder X-ray diffraction of lead tellurium glass powder of Comparative Example 5-1 measured in the same manner as in Example 1-1.
Looking at the X-ray diffraction results of the lead tellurium glass powder of Comparative Example 5 after the heat treatment, many crystalline peaks were observed. Each peak obtained by the automatic peak search was obtained by qualitative analysis, PbTeO 3 , ZnAl 2 O 4 , Pb 2 Te 3 O 8 , SiO 2 (α-SiO 2 ), Li 2 Al 2 Si 3 O 10 , LiAl 2 It was identified as due to O 4 and SiO 2. Therefore, peaks due to lead-containing oxides were detected.
次に、実施例１−１〜３−１の銀被覆鉛テルルガラス粉、比較例１−１〜４−１の鉛テルルガラス粉および比較例５−１の銀被覆鉛テルルガラス粉を用い、以下のようにして、導電性ペーストを作製した。 Next, the silver-coated lead tellurium glass powder of Examples 1-1 to 3-1, the lead tellurium glass powder of Comparative Examples 1-1 to 4-1 and the silver-coated lead tellurium glass powder of Comparative Example 5-1 were used. A conductive paste was prepared as follows.
（実施例１−２）
＜導電性ペーストの作製＞
実施例１−１の銀被覆鉛テルルガラス粉（銀含有量７．１質量％）１．８質量％、銀粉（ＡＧ−２．５−８Ｆ、ＤＯＷＡハイテック株式会社製）８９．１質量％、樹脂１（エチルセルロース１０ｃｐｓ、和光純薬工業株式会社製、３０質量％ブチルカルビトールアセテート溶液）０．４質量％、樹脂２（ＥＵ−５６３８、アクリル樹脂の４６．１質量％ブチルカルビトールアセテート溶液、日本カーバイド工業株式会社製）２．４質量％、溶剤１（商品名：ＣＳ−１２、化合物：テキサノール、ＪＮＣ株式会社製）１．６質量％、溶剤２（テキサノールとブチルカルビトールアセテートを１：１（質量比）で混合）４．０質量％、ステアリン酸マグネシウム（和光純薬工業株式会社製）０．２質量％、およびオレイン酸（和光純薬工業株式会社製）０．５質量％となるように秤量し、自公転式真空撹拌脱泡装置（あわとり練太郎、株式会社シンキー製）により混合（予備混練）した後、３本ロール（Ｍ−８０Ｓ、ＥＸＡＫＴ社製）により混練することにより、実施例１−２の導電性ペーストを得た。
得られた導電性ペーストについて、２５℃において粘度計（ブルックフィールド社製、ＨＢＤＶ−ＩＩＩ ＵＬＴＲＡ）にＣＰＥ−５２のコーンプレートを用いて１ｒｐｍの５分値と５ｒｐｍの１分値を測定し、２５℃における粘度を測定した。結果を表２に示した。
(Example 1-2)
<Preparation of conductive paste>
Silver-coated lead tellurium glass powder (silver content 7.1% by mass) 1.8% by mass, silver powder (AG-2.5-8F, manufactured by DOWA Hi-Tech Co., Ltd.) 89.1% by mass, Example 1-1, Resin 1 (ethyl cellulose 10 cps, manufactured by Wako Pure Chemical Industries, Ltd., 30 mass% butyl carbitol acetate solution) 0.4 mass%, resin 2 (EU-5638, 46.1 mass% butyl carbitol acetate solution of acrylic resin, Japan Carbide Industry Co., Ltd.) 2.4% by mass, solvent 1 (trade name: CS-12, compound: texanol, manufactured by JNC Co., Ltd.) 1.6% by mass, solvent 2 (texanol and butyl carbitol acetate 1: 1 (mixed by mass ratio)) 4.0% by mass, magnesium stearate (manufactured by Wako Pure Chemical Industries, Ltd.) 0.2% by mass, and oleic acid (manufactured by Wako Pure Chemical Industries, Ltd.) 0.5% by mass Weigh the masses so that they are mixed (preliminary kneading) with a self-rotating vacuum stirring defoaming device (Awatori Kentarou, manufactured by Shinky Co., Ltd.), and then knead with three rolls (M-80S, manufactured by EXAKT). Obtained the conductive paste of Example 1-2.
The obtained conductive paste was measured at 25 ° C. with a viscometer (HBDV-III ULTRA manufactured by Brookfield) using a CPE-52 cone plate to measure a 5-minute value at 1 rpm and a 1-minute value at 5 rpm. The viscosity at ° C was measured. The results are shown in Table 2.
（実施例２−２）
実施例１−２において、銀被覆鉛テルルガラス粉として実施例２−１の銀被覆鉛テルルガラス粉（銀含有量８．４質量％）１．８質量％を用い、銀粉をＡＧ−３−８ＦＤＩ（ＤＯＷＡハイテック株式会社製）９１．１質量％に代え、溶剤２（テキサノールとブチルカルビトールアセテートを１：１（質量比）で混合）を２．０質量％とした以外は、実施例１−２と同様にして実施例２−２の導電性ペーストを作製し、２５℃における粘度を測定した。結果を表２に示した。
(Example 2-2)
In Example 1-2, 1.8% by mass of the silver-coated lead tellurium glass powder (silver content 8.4% by mass) of Example 2-1 was used as the silver-coated lead tellurium glass powder, and the silver powder was used as AG-3-3. Example 1 except that solvent 2 (mixed with texanol and butyl carbitol acetate in a ratio of 1: 1 (mass ratio)) was set to 2.0% by mass instead of 8FDI (manufactured by DOWA Hightech Co., Ltd.) 91.1% by mass. The conductive paste of Example 2-2 was prepared in the same manner as in -2, and the viscosity at 25 ° C. was measured. The results are shown in Table 2.
（実施例３−２）
実施例１−２において、銀被覆鉛テルルガラス粉として実施例３−１の銀被覆鉛テルルガラス粉（銀含有量１０．０質量％）１．８質量％を用い、銀粉をＡＧ−４−８Ｆ（ＤＯＷＡハイテック株式会社製）９０．４７質量％に代え、ステアリン酸マグネシウムを０．３質量％とし、溶剤２（テキサノールとブチルカルビトールアセテートを１：１（質量比）で混合）を２．０質量％とした以外は、実施例１−２と同様にして実施例３−２の導電性ペーストを作製し、２５℃における粘度を測定した。結果を表２に示した。
(Example 3-2)
In Example 1-2, 1.8% by mass of the silver-coated lead tellurium glass powder (silver content 10.0% by mass) of Example 3-1 was used as the silver-coated lead tellurium glass powder, and the silver powder was AG-4-4. Instead of 8F (manufactured by DOWA Hightech Co., Ltd.) 90.47% by mass, magnesium stearate was added to 0.3% by mass, and solvent 2 (texanol and butyl carbitol acetate were mixed at a ratio of 1: 1 (mass ratio)) was added. A conductive paste of Example 3-2 was prepared in the same manner as in Example 1-2 except that it was set to 0% by mass, and the viscosity at 25 ° C. was measured. The results are shown in Table 2.
（比較例１−２）
実施例１−２において、銀被覆鉛テルルガラス粉に代えて比較例１−１の銀被覆していない鉛テルルガラス粉を１．７質量％とし、銀の量を合わせるために銀粉を８９．２質量％とした以外は、実施例１−２と同様にして比較例１−２の導電性ペーストを作製し、２５℃における粘度を測定した。結果を表２に示した。
(Comparative Example 1-2)
In Example 1-2, instead of the silver-coated lead tellurium glass powder, the silver-uncoated lead tellurium glass powder of Comparative Example 1-1 was 1.7% by mass, and the silver powder was 89. A conductive paste of Comparative Example 1-2 was prepared in the same manner as in Example 1-2 except that it was set to 2% by mass, and the viscosity at 25 ° C. was measured. The results are shown in Table 2.
（比較例２−２）
実施例２−２において、銀被覆鉛テルルガラス粉に代えて比較例２−１の銀被覆していない鉛テルルガラス粉を１．７質量％とし、銀の量を合わせるために銀粉を９１．２質量％とした以外は、実施例２−２と同様にして比較例２−２の導電性ペーストを作製し、２５℃における粘度を測定した。結果を表２に示した。
(Comparative Example 2-2)
In Example 2-2, instead of the silver-coated lead tellurium glass powder, the silver-uncoated lead tellurium glass powder of Comparative Example 2-1 was 1.7% by mass, and the silver powder was 91. A conductive paste of Comparative Example 2-2 was prepared in the same manner as in Example 2-2 except that it was set to 2% by mass, and the viscosity at 25 ° C. was measured. The results are shown in Table 2.
（比較例３−２）
実施例３−２において、銀被覆鉛テルルガラス粉に代えて比較例３−１の銀被覆していない鉛テルルガラス粉を１．６質量％とし、銀の量を合わせるために銀粉を９１．２５質量％とした以外は、実施例３−２と同様にして比較例３−２の導電性ペーストを作製し、２５℃における粘度を測定した。結果を表２に示した。
(Comparative Example 3-2)
In Example 3-2, instead of the silver-coated lead tellurium glass powder, the silver-uncoated lead tellurium glass powder of Comparative Example 3-1 was set to 1.6% by mass, and the silver powder was used to match the amount of silver. A conductive paste of Comparative Example 3-2 was prepared in the same manner as in Example 3-2 except that it was set to 25% by mass, and the viscosity at 25 ° C. was measured. The results are shown in Table 2.
（比較例４−２）
実施例１−２において、銀被覆鉛テルルガラス粉に代えて比較例４−１の銀被覆していない鉛テルルガラス粉を１．７質量％とし、銀の量を合わせるために銀粉を８９．２質量％とした以外は、実施例１−２と同様にして比較例４−２の導電性ペーストを作製し、２５℃における粘度を測定した。結果を表２に示した。
(Comparative Example 4-2)
In Example 1-2, instead of the silver-coated lead tellurium glass powder, the silver-uncoated lead tellurium glass powder of Comparative Example 4-1 was set to 1.7% by mass, and the silver powder was added to 89. A conductive paste of Comparative Example 4-2 was prepared in the same manner as in Example 1-2 except that it was set to 2% by mass, and the viscosity at 25 ° C. was measured. The results are shown in Table 2.
（比較例５−２）
実施例２−２において、銀被覆鉛テルルガラス粉として比較例５−１の銀被覆鉛テルルガラス粉を用いた以外は、実施例２−２と同様にして比較例５−２の導電性ペーストを作製し、２５℃における粘度を測定した。結果を表２に示した。
(Comparative Example 5-2)
In Example 2-2, the conductive paste of Comparative Example 5-2 was obtained in the same manner as in Example 2-2, except that the silver-coated lead tellurium glass powder of Comparative Example 5-1 was used as the silver-coated lead tellurium glass powder. Was prepared, and the viscosity at 25 ° C. was measured. The results are shown in Table 2.
表２より、実施例１−２および２−２にて銀被覆された鉛テルルガラスを用いた導電性ペーストは、比較例１−２および２−２の銀被覆していない鉛テルルガラスを用いた場合に比べて、粘度の低い導電性ペーストになることが分かった。
スクリーン印刷機での印刷では粘度が高いと印刷時の版抜け性やライン形状が悪くなり、低すぎるとにじみが発生するため、印刷性を合わせるために粘度を合わせての評価を行うことが必要となる。溶剤２を追添加することにより、全ての導電性ペーストの１ｒｐｍの５分値の粘度を、スクリーン印刷機での印刷が最適になる粘度範囲（例えば、３００ｒｐｍ±６０ｒｐｍ）でほぼ同じ値になるように調整した。調整に用いた溶剤の追加量およびその粘度の結果を表３に示した。
From Table 2, as the conductive paste using the silver-coated lead tellurium glass of Examples 1-2 and 2-2, the non-silver-coated lead tellurium glass of Comparative Examples 1-2 and 2-2 was used. It was found that the conductive paste had a lower viscosity than the case where it was used.
When printing with a screen printing machine, if the viscosity is high, the plate removal property and line shape at the time of printing will deteriorate, and if it is too low, bleeding will occur. It becomes. By adding the solvent 2, the viscosity of all the conductive pastes at 1 rpm for 5 minutes becomes almost the same value in the viscosity range (for example, 300 rpm ± 60 rpm) where printing with a screen printing machine is optimal. Adjusted to. Table 3 shows the results of the additional amount of the solvent used for the adjustment and its viscosity.
次に、得られた導電性ペーストを用い、以下のようにして、太陽電池を作製した。
（実施例１−３〜３−３および比較例１−３〜５−３）
＜太陽電池の作製＞
太陽電池用シリコン基板（１０５Ω／□）上に、スクリーン印刷機（ＭＴ−３２０Ｔ、マイクロテック社製）を用いて基板裏面に、アルミニウムペースト（アルソーラー１４−７０２１、東洋アルミニウム株式会社製）を用いて１５４ｍｍ□のベタパターンを形成した。
熱風乾燥機を用いて２００℃で１０分間乾燥させた。
基板表面に、各導電性ペーストを用いて４０μｍ幅のフィンガーと、１．３ｍｍ幅で、３本バスバーで設計したスクリーン版を用いて電極を形成した。
熱風乾燥機を用いて２００℃で１０分間乾燥させた。
高速焼成ＩＲ炉（日本碍子株式会社製）を用いて、ピーク時の温度（焼成温度）を８２０℃としてｉｎ−ｏｕｔ ２１ｓｅｃにて高速加熱した。以上により、太陽電池を作製した。なお、実施例３と比較例３においては、焼成温度を７５０℃とした。
Next, using the obtained conductive paste, a solar cell was produced as follows.
(Examples 1-3 to 3-3 and Comparative Examples 1-3 to 5-3)
<Manufacturing of solar cells>
A screen printing machine (MT-320T, manufactured by Microtech Co., Ltd.) is used on a silicon substrate for solar cells (105Ω / □), and an aluminum paste (Alsolar 14-7021, manufactured by Toyo Aluminum Co., Ltd.) is used on the back surface of the substrate. A solid pattern of 154 mm □ was formed.
It was dried at 200 ° C. for 10 minutes using a hot air dryer.
Electrodes were formed on the surface of the substrate using a finger having a width of 40 μm using each conductive paste and a screen plate having a width of 1.3 mm and designed with three bus bars.
It was dried at 200 ° C. for 10 minutes using a hot air dryer.
Using a high-speed firing IR furnace (manufactured by NGK Insulators, Ltd.), high-speed heating was performed in-out 21 sec with a peak temperature (firing temperature) of 820 ° C. From the above, a solar cell was manufactured. In Example 3 and Comparative Example 3, the firing temperature was set to 750 ° C.
＜太陽電池特性の評価＞
作製した太陽電池について、株式会社ワコム電創製ソーラーシミュレーターを用いて太陽電池特性を評価した。結果を表４に示した。
<Evaluation of solar cell characteristics>
The characteristics of the manufactured solar cells were evaluated using a solar simulator manufactured by Wacom Denso Co., Ltd. The results are shown in Table 4.
表４より、実施例１−１および実施例２−１の銀被覆鉛テルルガラスを用いた場合、銀被覆を有していない比較例１−１および比較例２−１の鉛テルルガラスに比べてペースト化したときに粘度を低くすることができ、さらに、適度な粘度に合わせる際に導電性ペースト中の銀含有量の低下を避けることができ（実施例１−２および実施例２−２）、太陽電池の変換効率が向上する効果があることが分かった（実施例１−３および実施例２−３）。
また、粘度の低減効果が小さくても、実施例３−３と比較例３−３の比較から明らかなように太陽電池の変換効率が向上する効果があることが分かった。
また、比較例４−３のようにテルルが４０質量％を超えて多い場合は、比較例１−３に比べ変換効率が低いことが分かった。
また、比較例５−３のように鉛を含む酸化物のピークが検出される場合には、直列抵抗が悪化して変換効率は１６．６９％まで減少していた。実施例１−３および実施例２−３との比較から、本発明の銀被覆による変換効率向上の効果は、鉛が結晶性の酸化物の状態で存在する場合には得られず、鉛がガラスの状態で存在することが必要であることが分かった。
From Table 4, when the silver-coated lead tellur glass of Examples 1-1 and 2-1 was used, it was compared with the lead tellur glass of Comparative Example 1-1 and Comparative Example 2-1 having no silver coating. The viscosity can be lowered when the paste is formed, and the silver content in the conductive paste can be avoided when the viscosity is adjusted to an appropriate level (Examples 1-2 and 2-2). ), It was found that there is an effect of improving the conversion efficiency of the solar cell (Examples 1-3 and 2-3).
Further, it was found that even if the effect of reducing the viscosity is small, there is an effect of improving the conversion efficiency of the solar cell, as is clear from the comparison between Example 3-3 and Comparative Example 3-3.
Further, it was found that when tellurium was more than 40% by mass as in Comparative Example 4-3, the conversion efficiency was lower than that in Comparative Example 1-3.
Further, when the peak of the oxide containing lead was detected as in Comparative Example 5-3, the series resistance deteriorated and the conversion efficiency decreased to 16.69%. From the comparison with Examples 1-3 and 2-3, the effect of improving the conversion efficiency by the silver coating of the present invention cannot be obtained when lead is present in the state of a crystalline oxide, and lead is not obtained. It turns out that it needs to be present in the state of glass.
本発明の銀被覆鉛テルルガラス粉は、種々の電子部品の電極や回路を形成するための導電性ペースト材料として、利用可能である。特に、太陽電池などの半導体電極用の導電性ペーストとして好適に利用可能である。 The silver-coated lead tellurium glass powder of the present invention can be used as a conductive paste material for forming electrodes and circuits of various electronic components. In particular, it can be suitably used as a conductive paste for semiconductor electrodes such as solar cells.
Claims (6)
前記鉛テルルガラス粉は、粉末Ｘ線回折において、リチウム、亜鉛、シリコン、およびアルミニウムから選ばれる２つ以上を含む酸化物のピークまたはビスマスを含む酸化物のピークが検出され、鉛を含む酸化物のピークが検出されないことを特徴とする銀被覆鉛テルルガラス粉。 A silver-coated lead-tellurium glass powder having a silver-coated layer on the surface of a lead-tellurium glass powder containing lead and tellurium and further containing two or more selected from lithium, zinc, silicon, aluminum, and bismuth.
In the lead tellurium glass powder, a peak of an oxide containing two or more selected from lithium, zinc, silicon, and aluminum or a peak of an oxide containing bismuth was detected by powder X-ray diffraction, and an oxide containing lead was detected. Silver-coated lead tellurium glass powder, characterized in that no peak is detected.
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