JP2017117955A - 光電変換素子の製造方法 - Google Patents
光電変換素子の製造方法 Download PDFInfo
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- JP2017117955A JP2017117955A JP2015252321A JP2015252321A JP2017117955A JP 2017117955 A JP2017117955 A JP 2017117955A JP 2015252321 A JP2015252321 A JP 2015252321A JP 2015252321 A JP2015252321 A JP 2015252321A JP 2017117955 A JP2017117955 A JP 2017117955A
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- photoelectric conversion
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- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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Abstract
【解決手段】正孔輸送層を電気化学重合法によって形成する。そして、正孔輸送層上に、金属酸化物およびペロブスカイト結晶を含む光電変換層を積層する。ここで、前記正孔輸送層上に、前記光電変換層を積層する際に、金属酸化物とペロブスカイト結晶の前駆体との溶液を、前記正孔輸送層上に塗布し、ついで、アニールすることによってペロブスカイト結晶を形成する。
【選択図】なし
Description
また、本発明者らは、上記知見を得た後、さらに検討を重ねて、本発明を完成させるに至った。
[1] 正孔輸送層と、金属酸化物およびペロブスカイト結晶を含む光電変換層とを少なくとも有する光電変換素子を製造する方法であって、前記正孔輸送層上に、前記光電変換層を形成することを特徴とする光電変換素子の製造方法。
[2] 正孔輸送層が第1の電極上に設けられている前記[1]記載の製造方法。
[3] 正孔輸送層がポリチオフェン誘導体を主成分として含む前記[1]または[2]に記載の製造方法。
[4] 金属酸化物が、酸化チタンである前記[1]〜[3]のいずれかに記載の製造方法。
[5] 金属酸化物が、多孔質体である前記[1]〜[4]のいずれかに記載の製造方法。
[6] ペロブスカイト結晶が、アニールにより形成される前記[1]〜[5]のいずれかに記載の製造方法。
[7] ペロブスカイト結晶が、結晶性半導体を主成分として含む前記[1]〜[6]のいずれかに記載の製造方法。
[8] ペロブスカイト結晶が、式:(RNH3)nPbX(2+n)(但し、Rは置換基を有していてもよい炭化水素基を示し、nは1または2を示し、XはI、BrまたはClを示す。)で表される化合物を主成分として含む前記[1]〜[7]のいずれかに記載の製造方法。
[9] 光電変換層を形成した後、前記光電変換層上に、電子輸送層を形成する前記[1]〜[8]のいずれかに記載の製造方法。
[10] 電子輸送層が、金属を主成分として含む請求項9記載の製造方法。
[11] 電子輸送層を形成した後、前記電子輸送層上に、第2の電極を形成する前記[9]または[10]に記載の製造方法。
[12] 前記[1]〜[11]のいずれかに記載の製造方法により製造された光電変換素子。
[13] 前記[12]記載の光電変換素子を含む太陽電池。
前記光電変換層は、金属酸化物およびペロブスカイト結晶を含んでさえいれば特に限定されない。
CH3NH3M1X3 ・・・(I)
(式中、M1は2価の金属イオンであり、Xは、F、Cl、BrまたはIである。)
(R6NH3)2M1X4 ・・・(II)
(式中、R6は炭素数2以上のアルキル基、アルケニル基、アラルキル基、アリール基、複素環基または芳香族複素環基であり、M1は2価の金属イオンであり、Xは、F、Cl、BrまたはIである。)
本発明においては、前記電子輸送層が金属を主成分として含むのが好ましく、2種以上の金属からなる合金であるのがより好ましく、Ga−In合金であるのが最も好ましい。
1.正孔輸送層の形成
ITO付ガラス板とステンレス板をスペーサー(厚さ1mm)を介してクリップで挟み、EDOT溶液中に浸し、GLASS/ITO基板を陽極につなぎ、ステンレス板を陰極につないで+0.5V〜20Vの直流電圧を印加することによって、電気化学重合を行い、PEDOTからなる正孔輸送層を形成した。なお、反応は室温で行い、反応条件は2V、5秒間とした。
TiO2とCH3NH3PbI3を混合して溶液を調製し、そのまま塗布、アニール(120℃、2分)することによって、いともたやすくナノサイズの酸化チタン上に CH3NH3PbI3のぺロブスカイト結晶を形成した。図1にアニールにより、ペロブスカイト結晶ができる様子を示す。図1(a)は、アニール前の様子を示し、図1(b)はアニール中の様子を示し、図1(c)はアニール後の様子を示す。図1から明らかな通り、アニール前は表面が黄色であったが、アニールにより黒くなったことが確認でき、目視でもペロブスカイト結晶が形成されていることがわかる。
上記2.で形成された光電変換層上に、常温で液体金属のGa−In合金を塗布して電子輸送層を形成した。
インジウム-スズ酸化物つきガラス(ITOガラス)基板を用いて、上記3.で形成された電子輸送層上に、電極としてITOを貼り合わせて、第2の電極を形成した。
上記2.で得られたペロブスカイト結晶につき、XRD回折装置を用いて、膜の同定を行った。結果を図2に示す。
また、上記4.で得られた光電変換素子につき、光応答性評価および解放端電圧測定を行った。結果を下記表1に示す。
第2の電極としてZnを用いたこと以外は、実施例1と同様にして光電変換素子を得た。得られた光電変換素子につき、光応答性評価および解放端電圧測定を行った。結果を下記表2に示す。
Claims (13)
- 正孔輸送層と、金属酸化物およびペロブスカイト結晶を含む光電変換層とを少なくとも有する光電変換素子を製造する方法であって、前記正孔輸送層上に、前記光電変換層を形成することを特徴とする光電変換素子の製造方法。
- 正孔輸送層が第1の電極上に設けられている請求項1記載の製造方法。
- 正孔輸送層がポリチオフェン誘導体を主成分として含む請求項1または2に記載の製造方法。
- 金属酸化物が、酸化チタンである請求項1〜3のいずれかに記載の製造方法。
- 金属酸化物が、多孔質体である請求項1〜4のいずれかに記載の製造方法。
- ペロブスカイト結晶が、アニールにより形成される請求項1〜5のいずれかに記載の製造方法。
- ペロブスカイト結晶が、結晶性半導体を主成分として含む請求項1〜6のいずれかに記載の製造方法。
- ペロブスカイト結晶が、式:(RNH3)nPbX(2+n)(但し、Rは置換基を有していてもよい炭化水素基を示し、nは1または2を示し、XはI、BrまたはClを示す。)で表される化合物を主成分として含む請求項1〜7のいずれかに記載の製造方法。
- 光電変換層を形成した後、前記光電変換層上に、電子輸送層を形成する請求項1〜8のいずれかに記載の製造方法。
- 電子輸送層が、金属を主成分として含む請求項9記載の製造方法。
- 電子輸送層を形成した後、前記電子輸送層上に、第2の電極を形成する請求項9または10に記載の製造方法。
- 請求項1〜11のいずれかに記載の製造方法により製造された光電変換素子。
- 請求項12記載の光電変換素子を含む太陽電池。
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