PowerPoint プレゼンテーション

A. Kojima, K. Teshima, Y. Shirai, T. Miyasaka

“Organometal halide perovskites as visible-light sensitizers for photovoltaic cells” J. Am. Chem. Soc. 2009, 131, 6050-6051.

■2008/12/9 (2009/4/14)

J.-H. Im, C.-R. Lee, J.-W. Lee, S.-W. Park, N.-G. Park

“6.5% efficient perovskite quantum-dot-sensitized solar cell” Nanoscale 2011, 3, 4088-4093.

■2011/7/19 (2011/8/15)

J.-H. Im, J. Chung, S.-J. Kim, N.-G. Park

“Synthesis, structure, and photovoltaic property of a nanocrystalline 2H perovskite-type novel sensitizer (CH₃CH₂NH₃)PbI₃”

Nanoscale Res. Lett. 2012, 7, 353/1-353/7. ■2012/5/22 (2012/6/28)

ペロブスカイト化合物を用いた太陽電池の報告例

電解液を用いたセル

1

L. Etgar, P. Gao, Z. Xue, Q. Peng, A. K. Chandiran, B. Liu, M. K. Nazeeruddin, M. Grätzel “Mesoscopic CH₃NH₃PbI₃/TiO₂ heterojunction solar cells”

J. Am. Chem. Soc. 2012, 134, 17396-17399. ■2012/8/6 (2012/10/8)

M. M. Lee, J. Teuscher, T. Miyasaka, T. N. Murakami, H. J. Snaith

“Efficient hybrid solar cells based on meso-superstructured organometal halide perovskites” Science 2012, 338, 643-647.

■2012/5/31 (2012/10/4)

H.-S. Kim, C.-R. Lee, J.-H. Im, K.-B. Lee, T. Moehl, A. Marchioro, S.-J. Moon, R. Humphry-Baker, J.-H. Yum, J. E. Moser, M. Grätzel, N.-G. Park

“Lead iodide perovskite sensitized all-solid-state submicron thin film mesoscopic solar cell with efficiency exceeding 9%”

Scientific Rep. 2012, 2, 591/1-591/7. ■2012/7/5 (2012/8/21)

J. H. Heo, S. H. Im, J. H. Noh, T. N. Mandal, C.-S. Lim, J. A. Chang, Y. H. Lee, H.-J. Kim, A. Sarkar, M. K. Nazeeruddin, M. Grätzel, S. I. Seok

“Efficient inorganic-organic hybrid heterojunction solar cells containing perovskite compound and polymeric hole conductors”

Nature Photonics 2013, 7, 486-491. ■2012/7/17 (2013/5/5)

全固体セルへの展開

－Scienceの論文が公表されるまで－

E. J. W. Crossland, N. Noel, V. Sivaram, T. Leijtens, J. A. Alexander-Webber, H. J. Snaith

“Mesoporous TiO₂ single crystals delivering enhanced mobility and optoelectronic device performance” Nature 2013, 495, 215-219.

■2012/12/11 (2013/3/6)

J. Qiu, Y. Qiu, K. Yan, M. Zhong, C. Mu, H. Yan, S. Yang

“All-solid-state hybrid solar cells based on a new organometal halide perovskite sensitizer and one-dimensional TiO₂ nanowire arrays”

Nanoscale 2013, 5, 3245-3248. ■2013/1/12 (2013/3/1)

H.-S. Kim, J.-W. Lee, N. Yantara, P. P. Boix, S. A. Kulkarni, S. Mhaisalkar, M. Grätzel, N.-G. Park “High efficiency solid-state sensitized solar cell-based on submicrometer rutile TiO₂ nanorod

and CH₃NH₃PbI₃ perovskite sensitizer” Nano Lett. 2013, 13, 2412-2417.

■2013/1/23 (2013/5/14)

J. H. Noh, S. H. Im, J. H. Heo, T. N. Mandal, S. I. Seok

“Chemical management for colorful, efficient, and stable inorganic-organic hybrid nanostructured solar cells”

Nano Lett. 2013, 13, 1764-1769. ■2013/1/28 (2013/3/21)

B. Cai, Y. Xing, Z. Yang, W.-H. Zhang, J. Qiu

“High performance hybrid solar cells sensitized by organolead halide perovskites” Energy Env. Sci. 2013, 6, 1480-1485.

■2013/1/30 (2013/3/11)

E. Edri, S. Kirmayer, D. Cahen, G. Hodes

“High open-circuit voltage solar cells based on organic-inorganic lead bromide perovskite” J. Phys. Chem. Lett. 2013, 4, 897-902.

■2013/2/15 (2013/2/28)

続々と発表された論文

－今年初めごろ－

J. M. Ball, M. M. Lee, A. Hey, H. J. Snaith

“Low-temperature processed meso-superstructured to thin-film perovskite solar cells” Energy Env. Sci. 2013, 6, 1739-1743.

■2013/3/8 (2013/3/27)

A. Abrusci, S. D. Stranks, P. Docampo, H.-L. Yip, A. K.-Y. Jen, H. J. Snaith

“High-performance perovskite-polymer hybrid solar cells via electronic coupling with fullerene monolayers” Nano Lett. 2013, 13, 3124-3128.

■2013/3/21 (2013/6/17)

D. Bi, L. Yang, G. Boschloo, A. Hagfeldt, E. M. J. Johansson

“Effect of different hole transport materials on recombination in CH₃NH₃PbI₃ perovskite-sensitized mesoscopic solar cells”

J. Phys. Chem. Lett. 2013, 4, 1532-1536. ■2013/3/22 (2013/4/12)

J.-Y. Jeng, Y.-F. Chiang, M.-H. Lee, S.-R. Peng, T.-F. Guo, P. Chen, T.-C. Wen “CH₃NH₃PbI₃ perovskite/fullerene planar-heterojunction hybrid solar cells” Adv. Mater. 2013, 25, 3727-3732.

■2013/3/25 (2013/6/17)

J. Burschka, N. Pellet, S.-J. Moon, R. Humphry-Baker, P. Gao, M. K. Nazeeruddin, M. Grätzel “Sequential deposition as a route to high-performance perovskite-sensitized solar cells”

Nature 2013, 499, 316-319. ■2013/4/3 (2013/7/10)

１５％論文の発表へ

“Organometal perovskite light absorbers toward a 20% efficiency low-cost solid-state mesoscopic solar cell” J. Phys. Chem. Lett. 2013, 4, 2423-2429.

■2013/4/27 (2013/7/11)

A. Kojima, K. Teshima, Y. Shirai, T. Miyasaka

“Organometal halide perovskites as visible-light sensitizers for photovoltaic cells” J. Am. Chem. Soc. 2009, 131, 6050-6051.

■2008/12/9 (2009/4/14)

J.-H. Im, C.-R. Lee, J.-W. Lee, S.-W. Park, N.-G. Park

“6.5% efficient perovskite quantum-dot-sensitized solar cell” Nanoscale 2011, 3, 4088-4093.

■2011/7/19 (2011/8/15)

J.-H. Im, J. Chung, S.-J. Kim, N.-G. Park

“Synthesis, structure, and photovoltaic property of a nanocrystalline 2H perovskite-type novel sensitizer (CH₃CH₂NH₃)PbI₃”

Nanoscale Res. Lett. 2012, 7, 353/1-353/7. ■2012/5/22 (2012/6/28)

A. Kojima, K. Teshima, Y. Shirai, T. Miyasaka

“Organometal halide perovskites as visible-light sensitizers for photovoltaic cells” J. Am. Chem. Soc. 2009, 131, 6050-6051.

ペロブスカイト化合物を増感剤として用いた太陽電池の最初の報告

有機色素に替えて、CdS、CdSe、PbS、InP、InAsなどの量子ドットを用いたものが報告されてきた。

これに対し、本研究では有機鉛ペロブスカイト化合物に着目した。

有機鉛ペロブスカイト化合物の外観

酸化チタン表面に吸着した

ナノ結晶ペロブスカイト化合物

ペロブスカイト化合物を用いた光電気化学セルの

IPCEスペクトル(左)と電流-電圧特性(右)

J.-H. Im, C.-R. Lee, J.-W. Lee, S.-W. Park, N.-G. Park

“6.5% efficient perovskite quantum-dot-sensitized solar cell” Nanoscale 2011, 3, 4088-4093. 7

スピンコートに用いる溶液の濃度を高くすることで変換効率が6.5%に上昇

酸化チタン表面に吸着した

ナノ結晶ペロブスカイト化合物

スピンコート溶液濃度を10, 20, 30, 40wt%と変化させた時の

電極外観、吸収スペクトル、電流-電圧特性、外部量子効率

最適化されたセルの特性

溶液濃度の他、

・作成後のアニール温度(40, 100, 160℃)

・酸化チタン膜厚(3.6, 5.5, 8.6 μm)

・酸化チタン表面の硝酸鉛による処理（効率6.2%→6.54%)

について検討。

8

J.-H. Im, J. Chung, S.-J. Kim, N.-G. Park

“Synthesis, structure, and photovoltaic property of a nanocrystalline 2H perovskite-type novel sensitizer (CH₃CH₂NH₃)PbI₃”

Nanoscale Res. Lett. 2012, 7, 353/1-353/7.

メチルアンモニウムの代わりにエチルアンモニウムを用いた例

酸化チタン表面に吸着した

ナノ結晶ペロブスカイト化合物 エネルギーレベルの考察 太陽電池特性

9

L. Etgar, P. Gao, Z. Xue, Q. Peng, A. K. Chandiran, B. Liu, M. K. Nazeeruddin, M. Grätzel “Mesoscopic CH₃NH₃PbI₃/TiO₂ heterojunction solar cells”

J. Am. Chem. Soc. 2012, 134, 17396-17399. ■2012/8/6 (2012/10/8)

M. M. Lee, J. Teuscher, T. Miyasaka, T. N. Murakami, H. J. Snaith

“Efficient hybrid solar cells based on meso-superstructured organometal halide perovskites” Science 2012, 338, 643-647.

■2012/5/31 (2012/10/4)

H.-S. Kim, C.-R. Lee, J.-H. Im, K.-B. Lee, T. Moehl, A. Marchioro, S.-J. Moon, R. Humphry-Baker, J.-H. Yum, J. E. Moser, M. Grätzel, N.-G. Park

“Lead iodide perovskite sensitized all-solid-state submicron thin film mesoscopic solar cell with efficiency exceeding 9%”

Scientific Rep. 2012, 2, 591/1-591/7. ■2012/7/5 (2012/8/21)

J. H. Heo, S. H. Im, J. H. Noh, T. N. Mandal, C.-S. Lim, J. A. Chang, Y. H. Lee, H.-J. Kim, A. Sarkar, M. K. Nazeeruddin, M. Grätzel, S. I. Seok

“Efficient inorganic-organic hybrid heterojunction solar cells containing perovskite compound and polymeric hole conductors”

Nature Photonics 2013, 7, 486-491. ■2012/7/17 (2013/5/5)

全固体セルへの展開

－Scienceの論文が公表されるまで－

酸化物多孔質膜は

アルミナでもよい

正孔輸送層は

なくてもよい

10.9%

9.7%

12.0%

5.5%

10

M. M. Lee, J. Teuscher, T. Miyasaka, T. N. Murakami, H. J. Snaith

“Efficient hybrid solar cells based on meso-superstructured organometal halide perovskites” Science 2012, 338, 643-647. Al₂O₃ planar構造セル 高効率Al2O3セル 高電圧 Al2O3セル TiO2セル

12

H.-S. Kim, C.-R. Lee, J.-H. Im, K.-B. Lee, T. Moehl, A. Marchioro, S.-J. Moon, R. Humphry-Baker, J.-H. Yum, J. E. Moser, M. Grätzel, N.-G. Park

“Lead iodide perovskite sensitized all-solid-state submicron thin film mesoscopic solar cell with efficiency exceeding 9%”

14

J. H. Heo, S. H. Im, J. H. Noh, T. N. Mandal, C.-S. Lim, J. A. Chang, Y. H. Lee, H.-J. Kim, A. Sarkar, M. K. Nazeeruddin, M. Grätzel, S. I. Seok

“Efficient inorganic-organic hybrid heterojunction solar cells containing perovskite compound and polymeric hole conductors”

Nature Photonics 2013, 7, 486-491.

ホール輸送層に高分子材料を用い、最高12%の変換効率を実現した。

PTAA:

15 100個のセルの変換効率の分布 34個のセルの変換効率の分布 (ホール輸送層：PTAA) (ホール輸送層： spiro-OMeTAD)

多数のセルの

中で、12%を

示したのは

1個/100個

16

L. Etgar, P. Gao, Z. Xue, Q. Peng, A. K. Chandiran, B. Liu, M. K. Nazeeruddin, M. Grätzel “Mesoscopic CH₃NH₃PbI₃/TiO₂ heterojunction solar cells”

J. Am. Chem. Soc. 2012, 134, 17396-17399.

17

E. J. W. Crossland, N. Noel, V. Sivaram, T. Leijtens, J. A. Alexander-Webber, H. J. Snaith

“Mesoporous TiO₂ single crystals delivering enhanced mobility and optoelectronic device performance” Nature 2013, 495, 215-219.

■2012/12/11 (2013/3/6)

J. Qiu, Y. Qiu, K. Yan, M. Zhong, C. Mu, H. Yan, S. Yang

“All-solid-state hybrid solar cells based on a new organometal halide perovskite sensitizer and one-dimensional TiO₂ nanowire arrays”

Nanoscale 2013, 5, 3245-3248. ■2013/1/12 (2013/3/1)

H.-S. Kim, J.-W. Lee, N. Yantara, P. P. Boix, S. A. Kulkarni, S. Mhaisalkar, M. Grätzel, N.-G. Park “High efficiency solid-state sensitized solar cell-based on submicrometer rutile TiO₂ nanorod

and CH₃NH₃PbI₃ perovskite sensitizer” Nano Lett. 2013, 13, 2412-2417.

■2013/1/23 (2013/5/14)

J. H. Noh, S. H. Im, J. H. Heo, T. N. Mandal, S. I. Seok

“Chemical management for colorful, efficient, and stable inorganic-organic hybrid nanostructured solar cells”

Nano Lett. 2013, 13, 1764-1769. ■2013/1/28 (2013/3/21)

B. Cai, Y. Xing, Z. Yang, W.-H. Zhang, J. Qiu

“High performance hybrid solar cells sensitized by organolead halide perovskites” Energy Env. Sci. 2013, 6, 1480-1485.

■2013/1/30 (2013/3/11)

E. Edri, S. Kirmayer, D. Cahen, G. Hodes

“High open-circuit voltage solar cells based on organic-inorganic lead bromide perovskite” J. Phys. Chem. Lett. 2013, 4, 897-902.

■2013/2/15 (2013/2/28)

続々と発表された論文

18

E. J. W. Crossland, N. Noel, V. Sivaram, T. Leijtens, J. A. Alexander-Webber, H. J. Snaith

“Mesoporous TiO₂ single crystals delivering enhanced mobility and optoelectronic device performance” Nature 2013, 495, 215-219.

メソポーラスな酸化チタン粒子を作製

19

J. Qiu, Y. Qiu, K. Yan, M. Zhong, C. Mu, H. Yan, S. Yang

“All-solid-state hybrid solar cells based on a new organometal halide perovskite sensitizer and one-dimensional TiO₂ nanowire arrays”

Nanoscale 2013, 5, 3245-3248.

20

H.-S. Kim, J.-W. Lee, N. Yantara, P. P. Boix, S. A. Kulkarni, S. Mhaisalkar, M. Grätzel, N.-G. Park “High efficiency solid-state sensitized solar cell-based on submicrometer rutile TiO₂ nanorod

and CH₃NH₃PbI₃ perovskite sensitizer” Nano Lett. 2013, 13, 2412-2417.

21

J. H. Noh, S. H. Im, J. H. Heo, T. N. Mandal, S. I. Seok

“Chemical management for colorful, efficient, and stable inorganic-organic hybrid nanostructured solar cells” Nano Lett. 2013, 13, 1764-1769.

BrとIの比率を変えて様々な色を出すと共に、

変換効率も最高12.3%を達成

22

B. Cai, Y. Xing, Z. Yang, W.-H. Zhang, J. Qiu

“High performance hybrid solar cells sensitized by organolead halide perovskites” Energy Env. Sci. 2013, 6, 1480-1485.

CH₃NH₃PbI₃ CH₃NH₃PbBr₃

23

E. Edri, S. Kirmayer, D. Cahen, G. Hodes

“High open-circuit voltage solar cells based on organic-inorganic lead bromide perovskite” J. Phys. Chem. Lett. 2013, 4, 897-902.

24

E. J. W. Crossland, N. Noel, V. Sivaram, T. Leijtens, J. A. Alexander-Webber, H. J. Snaith

“Mesoporous TiO₂ single crystals delivering enhanced mobility and optoelectronic device performance” Nature 2013, 495, 215-219.

■2012/12/11 (2013/3/6)

J. Qiu, Y. Qiu, K. Yan, M. Zhong, C. Mu, H. Yan, S. Yang

“All-solid-state hybrid solar cells based on a new organometal halide perovskite sensitizer and one-dimensional TiO₂ nanowire arrays”

Nanoscale 2013, 5, 3245-3248. ■2013/1/12 (2013/3/1)

H.-S. Kim, J.-W. Lee, N. Yantara, P. P. Boix, S. A. Kulkarni, S. Mhaisalkar, M. Grätzel, N.-G. Park “High efficiency solid-state sensitized solar cell-based on submicrometer rutile TiO₂ nanorod

and CH₃NH₃PbI₃ perovskite sensitizer” Nano Lett. 2013, 13, 2412-2417.

■2013/1/23 (2013/5/14)

J. H. Noh, S. H. Im, J. H. Heo, T. N. Mandal, S. I. Seok

“Chemical management for colorful, efficient, and stable inorganic-organic hybrid nanostructured solar cells”

Nano Lett. 2013, 13, 1764-1769. ■2013/1/28 (2013/3/21)

B. Cai, Y. Xing, Z. Yang, W.-H. Zhang, J. Qiu

“High performance hybrid solar cells sensitized by organolead halide perovskites” Energy Env. Sci. 2013, 6, 1480-1485.

■2013/1/30 (2013/3/11)

E. Edri, S. Kirmayer, D. Cahen, G. Hodes

“High open-circuit voltage solar cells based on organic-inorganic lead bromide perovskite” J. Phys. Chem. Lett. 2013, 4, 897-902.

■2013/2/15 (2013/2/28)

続々と発表された論文

25

J. M. Ball, M. M. Lee, A. Hey, H. J. Snaith

“Low-temperature processed meso-superstructured to thin-film perovskite solar cells” Energy Env. Sci. 2013, 6, 1739-1743.

■2013/3/8 (2013/3/27)

A. Abrusci, S. D. Stranks, P. Docampo, H.-L. Yip, A. K.-Y. Jen, H. J. Snaith

“High-performance perovskite-polymer hybrid solar cells via electronic coupling with fullerene monolayers” Nano Lett. 2013, 13, 3124-3128.

■2013/3/21 (2013/6/17)

D. Bi, L. Yang, G. Boschloo, A. Hagfeldt, E. M. J. Johansson

“Effect of different hole transport materials on recombination in CH₃NH₃PbI₃ perovskite-sensitized mesoscopic solar cells”

J. Phys. Chem. Lett. 2013, 4, 1532-1536. ■2013/3/22 (2013/4/12)

J.-Y. Jeng, Y.-F. Chiang, M.-H. Lee, S.-R. Peng, T.-F. Guo, P. Chen, T.-C. Wen “CH₃NH₃PbI₃ perovskite/fullerene planar-heterojunction hybrid solar cells” Adv. Mater. 2013, 25, 3727-3732.

■2013/3/25 (2013/6/17)

J. Burschka, N. Pellet, S.-J. Moon, R. Humphry-Baker, P. Gao, M. K. Nazeeruddin, M. Grätzel “Sequential deposition as a route to high-performance perovskite-sensitized solar cells”

Nature 2013, 499, 316-319. ■2013/4/3 (2013/7/10)

１５％論文の発表へ

“Organometal perovskite light absorbers toward a 20% efficiency low-cost solid-state mesoscopic solar cell” J. Phys. Chem. Lett. 2013, 4, 2423-2429.

26

J. M. Ball, M. M. Lee, A. Hey, H. J. Snaith

“Low-temperature processed meso-superstructured to thin-film perovskite solar cells” Energy Env. Sci. 2013, 6, 1739-1743.

プロセス温度を150℃以下にしつつ、

変換効率12.3%を達成

27

D. Bi, L. Yang, G. Boschloo, A. Hagfeldt, E. M. J. Johansson

“Effect of different hole transport materials on recombination in CH₃NH₃PbI₃ perovskite-sensitized mesoscopic solar cells”

J. Phys. Chem. Lett. 2013, 4, 1532-1536.

ホール輸送材料を替えると電子寿命が変わり、

最も長いspiroの時、変換効率が8.5%になった。

9.3Hz矩形波変調の460nmLEDで励起、 タングステン－ハロゲンランプでプローブ ホール輸送材料なしでは変化が小さいが、 おそらく電子移動は起こっている。 ホール輸送材料を加えると、ホール生成 を示す吸収が強く観測された。

28

A. Abrusci, S. D. Stranks, P. Docampo, H.-L. Yip, A. K.-Y. Jen, H. J. Snaith

“High-performance perovskite-polymer hybrid solar cells via electronic coupling with fullerene monolayers” Nano Lett. 2013, 13, 3124-3128.

フラーレン層を組み合わせた例

transient photocurrent decay

フラーレン層がないと、電子は酸化チタンに注入される。酸化チタン中の電子移動は遅い。 フラーレン層があると、電子はフラーレン層に留まり、熱的にペロブスカイト中に戻る。 ペロブスカイト中の電子移動は数桁早いので、こちらがメインになる。

transient photocurrent decayの違いは、これを反映している。

29

J.-Y. Jeng, Y.-F. Chiang, M.-H. Lee, S.-R. Peng, T.-F. Guo, P. Chen, T.-C. Wen “CH₃NH₃PbI₃ perovskite/fullerene planar-heterojunction hybrid solar cells” Adv. Mater. 2013, 25, 3727-3732.

31

PbI

/ DMF

TiO

FTO

CH

NH

I

/ 2-PrOH

逐次浸漬のイメージ

33

35

PbI

も いろいろな構造をとる

38

T. Baikie, Y. Fang, J. M. Kadro, M. Schreyer, F. Wei, S. G. Mhaisalkar, M. Graetzel, T. J. White

“Synthesis and crystal chemistry of the hybrid perovskite (CH

NH

)PbI

for solid-state sensitized

solar cell applications”

J. Mater. Chem. A 2013, 1, 5628-5641.

J. Chem. Phys. 1987, 87, 6373-6378.

結晶構造について詳しく調べ、バンド構造を考察

40

得られたバンド構造をもとに、