Electrochromic devices and fabrication methods
View Patent ↗An electrochromic device includes a first conductive layer, a single-layer or dual-layer ion conductor layer, and a second conductive layer. The layers are deposited using PVD, CVD, PECVD, atomic layer deposition, pulsed laser deposition, plating, or sol-gel techniques.
1. A method for forming an electrochromic device, comprising:
(a) forming a first conductive electrochromic layer;
(b) forming a first solid ion conductor layer having a thickness between about 1 nm and 300 nm over the first conductive layer, wherein the first solid ion conductor layer is formed using a deposition technique selected from the group consisting of sputtering, evaporation, CVD, PECVD, ALD, pulsed laser deposition, plating, and sol-gel;
(c) forming a second solid ion conductor layer having a thickness between about 1 nm and 300 nm on the first solid ion conductor layer, wherein the second solid ion conductor layer is formed from a different material than the first solid ion conductor layer, wherein the second solid ion conductor layer is formed using a deposition technique selected from the group consisting of sputtering, evaporation, CVD, PECVD, ALD, pulsed laser deposition, plating, and sol-gel, and no buffer layer is formed between the first solid ion conductor layer and the second solid ion conductor layer; and
(d) forming a second conductive counter electrode layer over the second solid ion conductor layer.
2. The method of claim 1 , wherein the first solid ion conductor layer includes a first material selected from the group consisting of Ta 2 O 5 , SiO 2 , Al 2 O 3 , Nb 2 O 3 , ZrO 2 , Li—Nb—O, Li—Ta—O, Li—Al—O, Li—P—O—N, Li—Ti—Al—P—O, Li—Si—Al—O, Li—Zn—Ge—O, Li—Si—P—O, Li—Zr—P—O, Li—La—Ti—O, B 2 O 3 , H 3 BO 3 , HBO 2 , H 2 B 4 O 7 , Bi 2 O 3 , CsHSO 4 , CsH 2 PO 4 , KH 2 PO 4 , KHSO 4 , and K 3 H(SO 4 ) 2 .
3. The method of claim 2 , wherein the second solid ion conductor layer includes a second material selected from the group consisting of a commonly used oxide such as Ta 2 O 5 , SiO 2 , Al 2 O 3 , Nb 2 O 3 , ZrO 2 , Li—Nb—O, Li—Ta—O, Li—Al—O, Li—P—O—N, Li—Ti—Al—P—O, Li—Si—Al—O, Li—Zn—Ge—O, Li—Si—P—O, Li—Zr—P—O, Li—La—Ti—O, B 2 O 3 , H 3 BO 3 , HBO 2 , H 2 B 4 O 7 , Bi 2 O 3 , CsHSO 4 , CsH 2 PO 4 , KH 2 PO 4 , KHSO 4 , and K 3 H(SO 4 ) 2 , and the second material is different from the first material.
4. The method of claim 3 , wherein the first solid ion conductor layer and the second solid ion conductor layer are each formed in selected atmospheres, wherein the selected atmospheres may be the same or different and are selected from the group consisting of water vapor, oxygen, and a mixture of water vapor and oxygen.
5. The method of claim 4 , wherein the first conductive layer is a counter-electrode layer, and the second conductive layer is an electrochromic layer.
6. The method of claim 1 , further comprising forming at least one additional ion conductor layer over the second solid ion conductor layer before forming the second conductive counter electrode layer, wherein each additional ion conductor layer is formed from a different material or using a different deposition technique than the previously formed ion conductor layer.
7. The method of claim 1 , wherein the first solid ion conductor layer has a thickness between 5 nm and 50 nm.
8. The method of claim 1 , wherein the second solid ion conductor layer has a thickness between 5 nm and 50 nm.
9. The method of claim 1 , wherein one of the ion conductor layers is a material that reduces degradation of at least one adjacent layer.
10. The method of claim 1 , further comprising providing ions for conduction through the ion conductor layers, wherein the provided ions include ions selected from the group consisting of hydrogen and lithium ions.
11. The method of claim 1 , wherein the first ion conductor layer includes a first material selected from the group consisting of hygroscopic materials and solid acids.
12. An electrochromic device, comprising:
(a) a first conductive electrochromic layer;
(b) a first solid ion conductor layer having a thickness between about 1 nm and 300 nm formed on the first conductive layer;
(c) a second solid ion conductor layer having a thickness between about 1 nm and 300 nm formed on the first solid ion conductor layer, wherein the second solid ion conductor is formed from a different material than the first solid ion conductor layer, no buffer layer being formed between the first solid ion conductor layer and the second solid ion conductor layer; and
(d) a second conductive counter electrode layer formed over the second solid ion conductor layer.
13. The electrochromic device of claim 12 , wherein the first solid ion conductor layer includes a first material selected from the group consisting of Ta 2 O 5 , SiO 2 , Al 2 O 3 , Nb 2 O 3 , ZrO 2 , Li—Nb—O, Li—Ta—O, Li—Al—O, Li—P—O—N, Li—Ti—Al—P—O, Li—Si—Al—O, Li—Zn—Ge—O, Li—Si—P—O, Li—Zr—P—O, Li—La—Ti—O, B 2 O 3 , H 3 BO 3 , HBO 2 , H 2 B 4 O 7 , Bi 2 O 3 , CsHSO 4 , CsH 2 PO 4 , KH 2 PO 4 , KHSO 4 , and K 3 H(SO 4 ) 2 .
14. The electrochromic device of claim 13 , wherein the solid second ion conductor layer includes a second material selected from the group consisting of Ta 2 O 5 , SiO 2 , Al 2 O 3 , Nb 2 O 3 , ZrO 2 , Li—Nb—O, Li—Ta—O, Li—Al—O, Li—P—O—N, Li—Ti—Al—P—O, Li—Si—Al—O, Li—Zn—Ge—O, Li—Si—P—O, Li—Zr—P—O, Li—La—Ti—O, B 2 O 3 , H 3 BO 3 , HBO 2 , H 2 B 4 O 7 , Bi 2 O 3 , CsHSO 4 , CsH 2 PO 4 , KH 2 PO 4 , KHSO 4 , and K 3 H(SO 4 ) 2 .
15. The electrochromic device of claim 14 , wherein the second solid ion conductor layer includes a plurality of sublayers of the second material, and adjacent sublayers of the second material are formed using different processing or deposition conditions.
16. The electrochromic device of claim 13 , wherein the first solid ion conductor layer includes a plurality of sublayers of the first material, and adjacent sublayers of the first material are formed using different processing or deposition conditions.
17. The electrochromic device of claim 16 , wherein the sublayers are formed using different atmospheres.
18. The electrochromic device of claim 17 , wherein the different atmospheres are selected from the group consisting of water vapor, oxygen, and a mixture of water vapor and oxygen.
19. The electrochromic device of claim 16 , wherein the second solid ion conductor layer includes a second material selected from the group consisting of Ta 2 O 5 , SiO 2 , Al 2 O 3 , Nb 2 O 3 , ZrO 2 , Li—Nb—O, Li—Ta—O, Li—Al—O, Li—P—O—N, Li—Ti—Al—P—O, Li—Si—Al—O, Li—Zn—Ge—O, Li—Si—P—O, Li—Zr—P—O, Li—La—Ti—O, B 2 O 3 , H 3 BO 3 , HBO 2 , H 2 B 4 O 7 , Bi 2 O 3 , CsHSO 4 , CsH 2 PO 4 , KH 2 PO 4 , KHSO 4 , and K 3 H(SO 4 ) 2 , the second material is different from the first material, the second conductor layer includes a plurality of sublayers of the second material, and adjacent sublayers of the second material are formed using different processing or deposition conditions.
20. The electrochromic device of claim 12 , further comprising at least one additional ion conductor layer between the second solid ion conductor layer and the second conductive counter electrode layer, wherein each additional ion conductor layer is formed from a different material or using a different deposition technique than the previously formed ion conductor layer.
21. The electrochromic device of claim 12 , wherein the first solid ion conductor layer has a thickness between 5 nm and 50 nm.
22. The electrochromic device of claim 12 , wherein the second solid ion conductor layer has a thickness between 5 nm and 50 nm.
23. The electrochromic device of claim 12 , wherein one of the ion conductor layers is a material that reduces degradation of at least one adjacent layer.
24. A method for forming an electrochromic device, comprising:
(a) forming a first conductive electrochromic layer;
(b) forming a first ion conductor layer having a thickness between about 1 nm and 300 nm over the first conductive layer, wherein the first ion conductor layer is formed using a deposition technique selected from the group consisting of sputtering, evaporation, CVD, PECVD, ALD, pulsed laser deposition, plating, and sol-gel, the first ion conductor layer including a first material selected from the group consisting of Ta 2 O 5 , SiO 2 , Al 2 O 3 , Nb 2 O 3 , ZrO 2 , Li—Nb—O, Li—Ta—O, Li—Al—O, Li—P—O—N, Li—Ti—Al—P—O, Li—Si—Al—O, Li—Zn—Ge—O, Li—Si—P—O, Li—Zr—P—O, Li—La—Ti—O, B 2 O 3 , H 3 BO 3 , HBO 2 , H 2 B 4 O 7 , Bi 2 O 3 , Mg 3 (PO 4 ) 2 .22H 2 O, MgHPO 4 .3H 2 O, KAISO 4 .12H 2 O, NaH 2 P 2 O 7 .6H 2 O, CsHSO 4 , CsH 2 PO 4 , KH 2 PO 4 , KHSO 4 , and K 3 H(SO 4 ) 2 ;
(c) forming a second ion conductor layer having a thickness between about 1 nm and 300 nm on the first ion conductor layer, wherein the second ion conductor layer is formed from a different material or using a different deposition technique than the first ion conductor layer, wherein the second ion conductor layer is formed using a deposition technique selected from the group consisting of sputtering, evaporation, CVD, PECVD, ALD, pulsed laser deposition, plating, and sol-gel, the second ion conductor layer including a second material selected from the group consisting of Ta 2 O 5 , SiO 2 , Al 2 O 3 , Nb 2 O 3 , ZrO 2 , Li—Nb—O, Li—Ta—O, Li—Al—O, Li—P—O—N, Li—Ti—Al—P—O, Li—Si—Al—O, Li—Zn—Ge—O, Li—Si—P—O, Li—Zr—P—O, Li—La—Ti—O, B 2 O 3 , H 3 BO 3 , HBO 2 , H 2 B 4 O 7 , Bi 2 O 3 , Mg 3 (PO 4 ) 2 .22H 2 O, MgHPO 4 .3H 2 O, KAISO 4 .12H 2 O, NaH 2 P 2 O 7 .6H 2 O, CsHSO 4 , CsH 2 PO 4 , KH 2 PO 4 , KHSO 4 , and K 3 H(SO 4 ) 2 , and the second material is different from the first material, and no buffer layer is formed between the first ion conductor layer and the second ion conductor layer; and
(d) forming a second conductive counter electrode layer over the second ion conductor layer.
25. The method of claim 24 , wherein the first ion conductor layer and the second ion conductor layer are each formed in selected atmospheres, and wherein the selected atmospheres may be the same or different and are selected from the group consisting of water vapor, oxygen, and a mixture of water vapor and oxygen.
26. The method of claim 25 , wherein the first conductive layer is a counter-electrode layer, and the second conductive layer is an electrochromic layer.
27. The method of claim 24 , further comprising forming at least one additional ion conductor layer over the second ion conductor layer before forming the second conductive counter electrode layer, each additional ion conductor layer being formed from a different material or using a different deposition technique than the previously formed ion conductor layer.
28. The method of claim 24 , wherein the first ion conductor layer has a thickness between 5 nm and 50 nm.
29. The method of claim 24 , wherein the second ion conductor layer has a thickness between 5 nm and 50 nm.
30. The method of claim 24 , wherein one of the ion conductor layers is a material that reduces degradation of at least one adjacent layer.
31. The method of claim 24 , further comprising providing ions for conduction through the ion conductor layers, wherein the provided ions include ions selected from the group consisting of hydrogen and lithium ions.
32. The method of claim 24 , wherein the first ion conductor layer includes a first material selected from the group consisting of hygroscopic materials and solid acids.
33. A method for forming an electrochromic device, comprising:
(a) forming a first conductive electrochromic layer;
(b) forming a first ion conductor layer having a thickness between about 1 nm and 300 nm over the first conductive layer, wherein the first ion conductor layer is formed using a deposition technique selected from the group consisting of sputtering, evaporation, CVD, PECVD, ALD, pulsed laser deposition, plating, and sol-gel;
(c) forming a second ion conductor layer having a thickness between about 1 nm and 300 nm on the first ion conductor layer, wherein the second ion conductor layer is formed from a different material or using a different deposition technique than the first ion conductor layer, wherein the second ion conductor layer is formed using a deposition technique selected from the group consisting of sputtering, evaporation, CVD, PECVD, ALD, pulsed laser deposition, plating, and sol-gel, the second ion conductor layer comprising a thickness between 5 nm and 50 nm, no buffer layer is formed between the first ion conductor layer and the second ion conductor layer; and
(d) forming a second conductive counter electrode layer over the second ion conductor layer.
34. An electrochromic device, comprising:
(a) a first conductive electrochromic layer;
(b) a first ion conductor layer having a thickness between about 1 nm and 300 nm formed over the first conductive layer, the first ion conductor layer including a first material selected from the group consisting of Ta 2 O 5 , SiO 2 , Al 2 O 3 , Nb 2 O 3 , ZrO 2 , Li—Nb—O, Li—Ta—O, Li—Al—O, Li—P—O—N, Li—Ti—Al—P—O, Li—Si—Al—O, Li—Zn—Ge—O, Li—Si—P—O, Li—Zr—P—O, Li—La—Ti—O, B 2 O 3 , H 3 BO 3 , HBO 2 , H 2 B 4 O 7 , Bi 2 O 3 , Mg 3 (PO 4 ) 2 .22H 2 O, MgHPO 4 .3H 2 O, KAISO 4 .12H 2 O, NaH 2 P 2 O 7 .6H 2 O, CsHSO 4 , CsH 2 PO 4 , KH 2 PO 4 , KHSO 4 , and K 3 H(SO 4 ) 2 ;
(c) a second ion conductor layer having a thickness between about 1 nm and 300 nm formed on the first ion conductor layer, wherein the second ion conductor is formed from a different material or using a different deposition technique than the first ion conductor layer, the second ion conductor layer including a second material selected from the group consisting of Ta 2 O 5 , SiO 2 , Al 2 O 3 , Nb 2 O 3 , ZrO 2 , Li—Nb—O, Li—Ta—O, Li—Al—O, Li—P—O—N, Li—Ti—Al—P—O, Li—Si—Al—O, Li—Zn—Ge—O, Li—Si—P—O, Li—Zr—P—O, Li—La—Ti—O, B 2 O 3 , H 3 BO 3 , HBO 2 , H 2 B 4 O 7 , Bi 2 O 3 , Mg 3 (PO 4 ) 2 .22H 2 O, MgHPO 4 .3H 2 O, KAISO 4 .12H 2 O, NaH 2 P 2 O 7 .6H 2 O, CsHSO4, CsH 2 PO 4 , KH 2 PO 4 , KHSO 4 , and K 3 H(SO 4 ) 2 , and no buffer layer is formed between the first ion conductor layer and the second ion conductor layer; and
(d) a second conductive counter electrode layer formed over the second ion conductor layer.
35. The electrochromic device of claim 34 , wherein the first ion conductor layer includes a plurality of sublayers of the first material, and adjacent sublayers of the first material are formed using different processing or deposition conditions.
36. The electrochromic device of claim 35 , wherein the sublayers are formed using different atmospheres.
37. The electrochromic device of claim 36 , wherein the different atmospheres are selected from the group consisting of water vapor, oxygen, and a mixture of water vapor and oxygen.
38. The electrochromic device of claim 34 , wherein the second ion conductor layer includes a plurality of sublayers of the second material, and adjacent sublayers of the second material are formed using different processing or deposition conditions.
39. The electrochromic device of claim 34 , further comprising at least one additional ion conductor layer between the second ion conductor layer and the second conductive counter electrode layer, wherein each additional ion conductor layer is formed from a different material or using a different deposition technique than the previously formed ion conductor layer.
40. The electrochromic device of claim 34 , wherein the first ion conductor layer has a thickness between 5 nm and 50 nm.
41. The electrochromic device of claim 34 , wherein the second ion conductor layer has a thickness between 5 nm and 50 nm.
42. The electrochromic device of claim 34 , wherein one of the ion conductor layers is a material that reduces degradation of at least one adjacent layer.
43. An electrochromic device, comprising:
(a) a first conductive electrochromic layer;
(b) a first ion conductor layer having a thickness between about 1 nm and 300 nm formed over the first conductive layer;
(c) a second ion conductor layer having a thickness between about 1 nm and 300 nm formed on the first ion conductor layer, wherein the second ion conductor is formed from a different material or using a different deposition technique than the first ion conductor layer, and the second ion conductor layer having a thickness between 5 nm and 50 nm, and no buffer layer is formed between the first ion conductor layer and the second ion conductor layer; and
(d) a second conductive counter electrode layer formed over the second ion conductor layer.