Organic solar cell device

Abstract

The invention relates to an organic solar cell device which comprises a first photoactive layer and a second photoactive layer, the first photoactive layer comprises an anode buffer layer material (SAMs) with anchoring groups and a polymer donor material, and collaborative optimization is achieved through material matching of the first photoactive layer and the second photoactive layer. And the photoelectric property of the device is improved.

Description

Technical Field

[0001] The invention relates to the field of organic solar cells, in particular to an organic solar cell device. Background Art

[0002] As an inexhaustible clean energy, solar energy has received widespread attention and has developed rapidly in recent years. Compared with inorganic solar cells, organic solar cells have the characteristics and advantages of flexibility, translucency, and large-area printing. They have broad application and development prospects in building and equipment integration, automotive glass, and wearable devices.

[0003] The device structure of a typical organic solar cell includes an anode, an anode buffer layer, a photoactive layer, a cathode buffer layer and a cathode stacked in sequence. The working principle of an organic solar cell is as follows: sunlight is incident on the photoactive layer, absorbed by the donor and the acceptor to generate excitons, which are separated into free charges - electrons and holes - at the donor / acceptor interface, and then transported to the negative and positive electrodes respectively, and then enter the cathode buffer layer and the anode buffer layer respectively. Finally, the electrons and holes are collected by the negative / positive electrodes to generate current and voltage. Therefore, the coordinated optimization of the materials of each functional layer is the key to achieving efficient charge transport.

[0004] The current anode buffer layer materials containing anchoring groups have simple molecular structures, are easy to synthesize, have high light transmittance, and have adjustable work functions, and have great application prospects in modifying electrodes. However, when the anode buffer layer materials (SAMs) containing anchoring groups are used as a single component in the anode buffer layer, the anode buffer layer based on SAMs is usually a very thin monolayer with a coverage density of about 10-15 molecules nm. -2 , which makes it difficult to form a uniform and stable thin film during preparation, limiting the photoelectric performance of organic solar cell devices. Summary of the invention

[0005] The object of the present invention is to provide an organic solar cell device structure, comprising a first photoactive layer and a second photoactive layer, wherein synergistic optimization is achieved through the material combination of the first photoactive layer and the second photoactive layer, thereby improving the photoelectric performance of the device.

[0006] To achieve the purpose of the present invention, the technical solution is as follows:

[0007] An organic solar cell device comprises a cathode, an anode, a first photoactive layer and a second photoactive layer located between the cathode and the anode, wherein: the first photoactive layer is located on the anode, and the second photoactive layer is located on the first photoactive layer; the first photoactive layer comprises a polymer P A and an anode buffer layer material containing an anchoring group, wherein the anchoring group is selected from any of the following groups:

[0008]

[0009] The polymer P A Selected from photoactive layer polymer donor materials.

[0010] In one embodiment, the anode buffer layer material containing an anchoring group is selected from the following general formula:

[0011]

[0012] Wherein: Ar1 is selected from an aromatic group having 6 to 30 carbon atoms which is substituted or unsubstituted by one or more R, or a heteroaromatic group having 6 to 30 ring atoms which is substituted or unsubstituted by one or more R;

[0013] Each occurrence of L is independently selected from a straight-chain alkyl group having 1 to 20 C atoms, a straight-chain alkoxy group having 1 to 20 C atoms, a straight-chain alkylthio group having 1 to 20 C atoms, a branched-chain alkyl group having 3 to 20 C atoms, a branched-chain alkoxy group having 3 to 20 C atoms, a branched-chain alkylthio group having 3 to 20 C atoms, an aromatic group having 6 to 20 carbon atoms which is unsubstituted or substituted by one or more R, a heteroaromatic group having 5 to 20 ring atoms which is unsubstituted or substituted by one or more R, or a group formed by a combination of the above groups;

[0014] Each occurrence of A is independently selected from the following groups:

[0015]

[0016] m is selected from 1, 2, 3 or 4;

[0017] * indicates the attachment site;

[0018] Each occurrence of R is independently selected from -D, -F, -Cl, -Br, -I, cyano, nitro, amino, straight-chain alkyl having 1 to 20 C atoms, straight-chain alkoxy having 1 to 20 C atoms, straight-chain alkylthio having 1 to 20 C atoms, branched-chain alkyl having 3 to 20 C atoms, branched-chain alkoxy having 3 to 20 C atoms, branched-chain alkylthio having 3 to 20 C atoms, aromatic groups having 6 to 20 carbon atoms, heteroaromatic groups having 5 to 20 ring atoms, or groups formed by combinations of the above groups.

[0019] Further, each occurrence of R is independently selected from -D, -F, -Cl, -Br, -I, cyano, nitro, amino, straight-chain alkyl having 1 to 10 C atoms, straight-chain alkoxy having 1 to 10 C atoms, straight-chain alkylthio having 1 to 10 C atoms, branched-chain alkyl having 3 to 10 C atoms, branched-chain alkoxy having 3 to 10 C atoms, branched-chain alkylthio having 3 to 10 C atoms, aromatic groups having 6 to 10 carbon atoms, heteroaromatic groups having 5 to 10 ring atoms, or groups formed by combinations of the above groups.

[0020] In a specific embodiment, each occurrence of R is independently selected from -D, -F, -Cl, -Br, -I, cyano, nitro, -CF3, methyl, ethyl, isopropyl, tert-butyl, methoxy, ethoxy, methylthio, ethylthio, phenyl, diphenylamino, R a Substituted phenyl, R a Substituted diphenylamine; wherein R a Each occurrence is independently selected from -D, -F, -Cl, -Br, -I, cyano, nitro, -CF3, methyl, ethyl, isopropyl, tert-butyl, methoxy, ethoxy, methylthio, ethylthio or phenyl.

[0021] In one embodiment, each occurrence of L is independently selected from a linear alkyl group having 1 to 10 C atoms, a branched alkyl group having 3 to 10 C atoms, a # A substituted or unsubstituted aromatic group having 6 to 10 carbon atoms, replaced by one or more R # A substituted or unsubstituted heteroaromatic group having 5 to 10 ring atoms, or a group formed by a combination of the above groups;

[0022] Where R # Each occurrence is independently selected from -D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1 to 10 C atoms, straight-chain alkoxy having 1 to 10 C atoms, straight-chain alkylthio having 1 to 10 C atoms, branched-chain alkyl having 3 to 10 C atoms, branched-chain alkoxy having 3 to 10 C atoms, branched-chain alkylthio having 3 to 10 C atoms, aromatic groups having 6 to 10 carbon atoms, heteroaromatic groups having 5 to 10 ring atoms, or groups formed by combinations of the above groups.

[0023] In one embodiment, each occurrence of L is independently selected from -CH2-, -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH2-CH2-CH2-, -CH2-CH2-CH2-CH2-CH2-, -CH2-CH2-CH2-CH2-CH2-, -CH2-CH2-CH2-CH2-CH2-CH2-, -CH2-CH2-CH2-CH2-CH2-CH2-, -CH2-CH2-CH2-CH2-CH2-CH2-CH2-, -CH2-CH2-CH2-CH2-CH2-CH2-CH2-, CH2-CH2-CH2-CH2-CH2-CH2-, CH2-CH2-CH2-CH2-CH2-CH2-, CH2-CH2-CH2-CH2-CH2-CH2-, CH2-CH2-CH2-CH2-CH2-, CH2-CH2-CH2-CH2-CH2-, CH2-CH2-CH2-CH2-CH2-, CH2-CH2-CH2-CH2-CH2-, CH2-CH2-CH2-CH2-CH2-, CH2-CH2-CH2-CH2-CH2-, CH2-CH2-CH2-CH2-CH2-, CH2- b Substituted phenyl, unsubstituted or replaced by R b substituted pyridyl, unsubstituted or replaced by R b Substituted pyrimidinyl, unsubstituted or replaced by R b Substituted triazine, unsubstituted or replaced by R b Substituted benzothiadiazolyl, unsubstituted or replaced by R b Substituted biphenyl, unsubstituted or replaced by R b Substituted phenyl biphenylthiadiazolyl, unsubstituted or replaced by R b Substituted phenylbiphenylthiadiazolylbiphenyl; R b Each occurrence is independently selected from -D, -F, -Cl, -Br, -I, cyano, nitro, -CF3, or a straight chain alkyl group having 1-6 C atoms, or a branched chain alkyl group having 3-6 C atoms.

[0024] In a specific embodiment, the -LA is preferably selected from any of the following structures, but is not limited thereto:

[0025]

[0026]

[0027] In one embodiment, Ar1 is selected from the following structures:

[0028]

[0029] in:

[0030] Ar2, Ar3, Ar4 are independently selected from aromatic groups having 6 to 20 carbon atoms which are substituted or unsubstituted by one or more R, or heteroaromatic groups having 6 to 20 ring atoms which are substituted or unsubstituted by one or more R;

[0031] Each occurrence is independently selected from absence, a single bond,

[0032] Each occurrence is independently selected from a single bond,

[0033] R1, R2, R3, each occurrence, is independently selected from -H, -D, a straight-chain alkyl group having 1 to 20 C atoms, a straight-chain alkoxy group having 1 to 20 C atoms, a straight-chain alkylthio group having 1 to 20 C atoms, a branched-chain alkyl group having 3 to 20 C atoms, a branched-chain alkoxy group having 3 to 20 C atoms, a branched-chain alkylthio group having 3 to 20 C atoms, an aromatic group having 6 to 20 carbon atoms, a heteroaromatic group having 5 to 20 ring atoms, or a group formed by a combination of the above groups;

[0034] R2 and R3 may or may not form a ring with each other;

[0035] It represents the connection site between Ar1 and -LA.

[0036] In a specific embodiment, each occurrence of R1 is independently selected from an aromatic group having 6-10 carbon atoms which is substituted or unsubstituted by one or more R, or a heteroaromatic group having 6-10 ring atoms which is substituted or unsubstituted by one or more R.

[0037] In a specific embodiment, each occurrence of R2 and R3 is independently selected from -H, -D, a straight chain alkyl group having 1 to 10 C atoms, a branched chain alkyl group having 3 to 10 C atoms, an aromatic group having 6 to 10 carbon atoms substituted or unsubstituted by one or more R, or a heteroaromatic group having 6 to 10 ring atoms substituted or unsubstituted by one or more R. Further, each occurrence of R2 and R3 is independently selected from -H, -D, a straight chain alkyl group having 1 to 6 C atoms, a branched chain alkyl group having 3 to 6 C atoms, or a phenyl group substituted or unsubstituted by one or more R.

[0038] In one embodiment, Ar2, Ar3, and Ar4 are independently selected from aromatic groups having 6-10 carbon atoms which are substituted or unsubstituted by one or more R, or heteroaromatic groups having 6-10 ring atoms which are substituted or unsubstituted by one or more R.

[0039] Further, Ar2, Ar3, Ar4 are independently selected from any of the following groups:

[0040]

[0041] in:

[0042] Each occurrence of X is independently selected from C, CR4 or N;

[0043] R4 is independently selected at each occurrence from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, amino, straight-chain alkyl having 1 to 20 C atoms, straight-chain alkoxy having 1 to 20 C atoms, straight-chain alkylthio having 1 to 20 C atoms, branched-chain alkyl having 3 to 20 C atoms, branched-chain alkoxy having 3 to 20 C atoms, branched-chain alkylthio having 3 to 20 C atoms, aromatic groups having 6 to 20 carbon atoms, heteroaromatic groups having 5 to 20 ring atoms, or groups formed by combinations of the above groups;

[0044] When X is a fusion site, X is selected from C.

[0045] In one embodiment, Ar2 and Ar3 are independently selected from any of the following groups:

[0046]

[0047] Wherein: # represents a fusion site, and the fusion site is selected from C.

[0048] In one embodiment, the Ar4 is independently selected from the following groups:

[0049]

[0050] Wherein: # represents a fusion site, and the fusion site is selected from C.

[0051] Furthermore, the (B-1) is preferably selected from any of the following structures:

[0052]

[0053] In one embodiment, R2 and R3 do not form a ring with each other.

[0054] In another embodiment, R2 and R3 mutually form a 6-membered ring; and (B-1) is selected from the following structures:

[0055]

[0056] Wherein: W has the same meaning as described above.

[0057] In one embodiment, the (B-1) is preferably selected from any of the following structures:

[0058]

[0059] in: Each occurrence is independently selected from

[0060] Each occurrence is independently selected from a single bond, Furthermore, the (B-2) is preferably selected from any of the following structures:

[0061]

[0062] Preferably, W in (C-16)-(C-18) is selected from a single bond, Furthermore, the (B-3) is preferably selected from any of the following structures:

[0063]

[0064] Preferably, W in (C-19)-(C-21) is selected from a single bond,

[0065] Furthermore, the (B-4) is preferably selected from any of the following structures:

[0066]

[0067] Preferably, W in (C-22)-(C-24) is selected from a single bond,

[0068] In one embodiment, each occurrence of X is independently selected from CR4; each occurrence of R4 is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, amino, straight-chain alkyl having 1 to 10 C atoms, straight-chain alkoxy having 1 to 10 C atoms, straight-chain alkylthio having 1 to 10 C atoms, branched-chain alkyl having 3 to 10 C atoms, branched-chain alkoxy having 3 to 10 C atoms, branched-chain alkylthio having 3 to 10 C atoms, aromatic groups having 6 to 10 carbon atoms which are unsubstituted or substituted by one or more R, heteroaromatic groups having 5 to 10 ring atoms which are unsubstituted or substituted by one or more R, or a group formed by a combination of the above groups.

[0069] Further, each occurrence of X is independently selected from CR4; each occurrence of R4 is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl with 1 to 6 C atoms, straight-chain alkoxy with 1 to 6 C atoms, straight-chain alkylthio with 1 to 6 C atoms, branched-chain alkyl with 3 to 6 C atoms, branched-chain alkoxy with 3 to 6 C atoms, branched-chain alkylthio with 3 to 6 C atoms, one or more R c A substituted or unsubstituted aromatic group having 6 to 10 carbon atoms, replaced by one or more R c a substituted or unsubstituted heteroaromatic group having 5 to 10 ring atoms;

[0070] The substituent R cThe group is selected from -D, -F, -Cl, -Br, -I, cyano, nitro, amino, a straight-chain alkyl group having 1 to 10 C atoms, a straight-chain alkoxy group having 1 to 10 C atoms, a straight-chain alkylthio group having 1 to 10 C atoms, a branched-chain alkyl group having 3 to 10 C atoms, a branched-chain alkoxy group having 3 to 10 C atoms, a branched-chain alkylthio group having 3 to 10 C atoms, an aromatic group having 6 to 10 carbon atoms, a heteroaromatic group having 5 to 10 ring atoms, or a group formed by a combination of the above groups.

[0071] In one embodiment, when R4 is selected from an amino group, the R4 is selected from an unsubstituted or substituted d Substituted amino group, the R d Each occurrence is independently selected from straight-chain alkyl having 1 to 10 C atoms, branched-chain alkyl having 3 to 10 C atoms, unsubstituted or replaced by R e Substituted aromatic groups having 6 to 20 carbon atoms, unsubstituted or replaced by R e A substituted heteroaromatic group having 6 to 20 ring atoms; wherein R e Each occurrence is independently selected from -D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1 to 10 C atoms, straight-chain alkoxy having 1 to 10 C atoms, straight-chain alkylthio having 1 to 10 C atoms, branched-chain alkyl having 3 to 10 C atoms, branched-chain alkoxy having 3 to 10 C atoms, branched-chain alkylthio having 3 to 10 C atoms, aromatic groups having 6 to 10 carbon atoms, heteroaromatic groups having 5 to 10 ring atoms, or groups formed by combinations of the above groups.

[0072] In a specific embodiment, Ar1 is selected from the following structures, but is not limited thereto:

[0073]

[0074] Wherein: n1 is independently selected from 0, 1, 2, 3 or 4; n2 is independently selected from 0, 1, 2, 3, 4 or 5;

[0075] n3 is independently selected from 0, 1, 2, 3, 4, 5 or 6; n4 is independently selected from 0, 1 or 2.

[0076] In a specific embodiment, each occurrence of R4 is independently selected from -D, -F, -Cl, -Br, -I, cyano, nitro, -CF3, methyl, ethyl, isopropyl, tert-butyl, methoxy, ethoxy, methylthio, ethylthio, phenyl, diphenylamino, R f Substituted phenyl, R f Substituted diphenylamine; wherein R fEach occurrence is independently selected from -D, -F, -Cl, -Br, -I, cyano, nitro, -CF3, methyl, ethyl, isopropyl, tert-butyl, methoxy, ethoxy, methylthio, ethylthio or phenyl.

[0077] In a preferred embodiment, the anode buffer layer material containing an anchoring group is selected from any of the following structural formulas, but is not limited thereto:

[0078]

[0079]

[0080]

[0081] In one embodiment, the polymer P A Select from any of the following structures:

[0082]

[0083] Wherein: Ar5, Ar6 each time appears, independently selected from one or more R x A substituted or unsubstituted aromatic group having 6 to 30 carbon atoms, replaced by one or more R x A substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms, substituted by one or more R x a substituted or unsubstituted non-aromatic heterocycle having 5 to 30 ring atoms;

[0084] R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 Each occurrence is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1-20 carbon atoms, straight-chain alkoxy having 1-20 carbon atoms, straight-chain alkylthio having 1-20 carbon atoms, straight-chain ester having 1-20 carbon atoms, branched-chain alkyl having 3-20 carbon atoms, branched-chain alkoxy having 3-20 carbon atoms, branched-chain alkylthio having 3-20 carbon atoms, branched-chain ester having 3-20 carbon atoms, or a group formed by a combination of the above groups;

[0085] The R xEach occurrence is independently selected from: -D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1-20 carbon atoms, straight-chain alkoxy having 1-20 carbon atoms, straight-chain alkylthio having 1-20 carbon atoms, straight-chain ester having 1-20 carbon atoms, branched-chain alkyl having 3-20 carbon atoms, branched-chain alkoxy having 3-20 carbon atoms, branched-chain alkylthio having 3-20 carbon atoms, branched-chain ester having 3-20 carbon atoms, aromatic having 6-20 carbon atoms, heteroaromatic having 5-20 ring atoms, or a combination thereof;

[0086] n is the number of repeating units and is selected from integers greater than 1.

[0087] In one embodiment, each occurrence of Ar5 is independently selected from one or more R x A substituted or unsubstituted aromatic group having 6 to 20 carbon atoms, replaced by one or more R x A substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms, substituted by one or more R x A substituted or unsubstituted non-aromatic heterocycle having 5 to 20 ring atoms.

[0088] In one embodiment, the “being one or more R x The substituted or unsubstituted non-aromatic heterocycle having 5 to 20 ring atoms is selected from Where R 108 Each occurrence is independently selected from a straight chain alkyl group having 1 to 20 carbon atoms, or a branched chain alkyl group having 3 to 20 carbon atoms. 108 Each time a selection is made

[0089] Furthermore, the polymer P A You can choose from the following structures:

[0090]

[0091] In one embodiment, the “being one or more R x The substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms is selected from any of the following groups:

[0092]

[0093] Wherein: Y is selected from O, S, Se;

[0094] Each occurrence of V is independently selected from CR 110 or N;

[0095] R 109Each occurrence is independently selected from -H, -D, a straight chain alkyl group having 1 to 10 carbon atoms, or a branched chain alkyl group having 3 to 10 carbon atoms;

[0096] R 110 Each occurrence is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1-20 carbon atoms, straight-chain alkoxy having 1-20 carbon atoms, straight-chain alkylthio having 1-20 carbon atoms, straight-chain ester having 1-20 carbon atoms, branched-chain alkyl having 3-20 carbon atoms, branched-chain alkoxy having 3-20 carbon atoms, branched-chain alkylthio having 3-20 carbon atoms, branched-chain ester having 3-20 carbon atoms, or a group formed by a combination of the above groups.

[0097] Furthermore, the polymer P A You can choose from any of the following structures:

[0098]

[0099]

[0100] In one embodiment, the R 101 Each occurrence is independently selected from a branched chain alkyl having 3 to 16 carbon atoms, a branched chain alkoxy having 3 to 16 carbon atoms, or a branched chain alkylthio having 3 to 16 carbon atoms.

[0101] Furthermore, R 101 Each occurrence is independently selected from any of the following structures, but not limited to:

[0102]

[0103] In one embodiment, the R 102 Each occurrence is independently selected from -H (hydrogen), -D (deuterium), -F, -Cl, -Br, -I, -CF3, cyano, a straight chain alkyl group having 1-10 carbon atoms, or a branched or cyclic alkyl group having 3-10 carbon atoms.

[0104] In one embodiment, the R 103 Each occurrence is independently selected from -H (hydrogen), -D (deuterium), -F, -Cl, -Br, -I, -CF3, cyano, a straight chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms. Further, the R 103 Each occurrence is independently selected from -H (hydrogen), -D (deuterium), -F, -Cl, -Br, -I, -CF3, or cyano.

[0105] In one embodiment, Each occurrence is independently selected from any of the following groups:

[0106]

[0107] In one embodiment, Ar6 is selected from any of the following groups:

[0108]

[0109] Wherein: W1 is independently selected from O, S, Se at each occurrence; preferably, W1 is selected from S;

[0110] R 111 , R 112 , R 113 Each occurrence is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1-20 carbon atoms, straight-chain alkoxy having 1-20 carbon atoms, straight-chain alkylthio having 1-20 carbon atoms, straight-chain ester having 1-20 carbon atoms, branched-chain alkyl having 3-20 carbon atoms, branched-chain alkoxy having 3-20 carbon atoms, branched-chain alkylthio having 3-20 carbon atoms, branched-chain ester having 3-20 carbon atoms, or a group formed by a combination of the above groups;

[0111] R 114 , R 115 , R 116 Each occurrence is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1-20 carbon atoms, straight-chain alkoxy having 1-20 carbon atoms, straight-chain alkylthio having 1-20 carbon atoms, straight-chain ester having 1-20 carbon atoms, branched-chain alkyl having 3-20 carbon atoms, branched-chain alkoxy having 3-20 carbon atoms, branched-chain alkylthio having 3-20 carbon atoms, branched-chain ester having 3-20 carbon atoms, unsubstituted or replaced by one or more R y Substituted aromatic groups having 6 to 10 carbon atoms, unsubstituted or replaced by one or more R y A substituted heteroaromatic group having 5 to 10 ring atoms, or a group formed by a combination of the above groups;

[0112] The R yEach occurrence is independently selected from: -D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1-20 carbon atoms, straight-chain alkoxy having 1-20 carbon atoms, straight-chain alkylthio having 1-20 carbon atoms, straight-chain alkoxycarboxyl having 1-20 carbon atoms, branched-chain alkyl having 3-20 carbon atoms, branched-chain alkoxy having 3-20 carbon atoms, branched-chain alkylthio having 3-20 carbon atoms, branched-chain alkoxycarboxyl having 3-20 carbon atoms, or a group formed by a combination of the above groups.

[0113] Furthermore, the polymer P A You can choose from any of the following structures:

[0114]

[0115] In one embodiment, the R 111 Each occurrence is independently selected from a branched chain alkyl having 3 to 16 carbon atoms, a branched chain alkoxy having 3 to 16 carbon atoms, or a branched chain alkylthio having 3 to 16 carbon atoms.

[0116] Furthermore, R 111 Each occurrence is independently selected from any of the following structures, but not limited to:

[0117]

[0118] In one embodiment, the R 112 Each occurrence is independently selected from -H (hydrogen), -D (deuterium), -F, -Cl, -Br, -I, -CF3, cyano, a straight chain alkyl group having 1-10 carbon atoms, or a branched or cyclic alkyl group having 3-10 carbon atoms.

[0119] In one embodiment, the R 113 Each occurrence is independently selected from -H (hydrogen), -D (deuterium), -F, -Cl, -Br, -I, -CF3, cyano, a straight chain alkyl group having 1-10 carbon atoms, or a branched or cyclic alkyl group having 3-10 carbon atoms.

[0120] Furthermore, the R 113 Each occurrence is independently selected from -H (hydrogen), -D (deuterium), -F, -Cl, -Br, -I, -CF3, or cyano.

[0121] In one embodiment, the R 114 Each occurrence is independently selected from -H (hydrogen), -D (deuterium), -F, -Cl, -Br, -I, -CF3, cyano; further, in one embodiment, R 114 Each occurrence is independently selected from -H (hydrogen), or -F.

[0122] In one embodiment, the R 115 Each occurrence is independently selected from a straight chain alkoxy group having 1 to 20 carbon atoms, a branched chain alkoxy group having 3 to 20 carbon atoms, a y Substituted aromatic groups having 6 to 10 carbon atoms, or one or more R y Substituted heteroaromatic group having 5-10 ring atoms; R y Each occurrence is independently selected from straight chain alkoxy having 1 to 20 carbon atoms, branched chain alkoxy having 3 to 20 carbon atoms.

[0123] In one embodiment, the R 116 Each occurrence is independently selected from -H (hydrogen), -D (deuterium), -F, -Cl, -Br, -I, -CF3, cyano, straight chain alkyl having 1-10 carbon atoms, straight chain alkoxy having 1-10 carbon atoms, straight chain alkylthio having 1-10 carbon atoms, straight chain alkoxycarboxyl having 1-10 carbon atoms, branched chain alkyl having 3-10 carbon atoms, branched chain alkoxy having 3-10 carbon atoms, branched chain alkylthio having 3-10 carbon atoms, branched chain alkoxycarboxyl having 3-10 carbon atoms, unsubstituted or replaced by one or more R y Substituted aromatic groups having 6 to 10 carbon atoms, unsubstituted or replaced by one or more R y A substituted heteroaromatic group having 5 to 10 ring atoms, or a group formed by a combination of the above groups.

[0124] In one embodiment, the R 106 , R 107 Each occurrence is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1-20 carbon atoms, straight-chain alkoxy having 1-20 carbon atoms, straight-chain alkylthio having 1-20 carbon atoms, straight-chain ester having 1-20 carbon atoms, branched-chain alkyl having 3-20 carbon atoms, branched-chain alkoxy having 3-20 carbon atoms, branched-chain alkylthio having 3-20 carbon atoms, branched-chain ester having 3-20 carbon atoms, or a group formed by a combination of the above groups.

[0125] In a specific embodiment, the polymer P A Preferably, one, two or more of the following structural formulas are selected, but not limited thereto:

[0126]

[0127]

[0128] In one embodiment, the polymer P AThe mass ratio of the anode buffer layer material containing the anchoring group is selected from 1:1 to 200:1; preferably, the mass ratio is selected from 10:1 to 100:1.

[0129] In one embodiment, the first photoactive layer does not contain a photoactive layer receptor material. The photoactive layer receptor material is further described as follows.

[0130] In one embodiment, the first photoactive layer is composed of a polymer P A and an anode buffer layer material containing an anchoring group.

[0131] In one embodiment, according to the organic solar cell device of the present invention, the anode layer is closely stacked with the first photoactive layer, and the second photoactive layer is closely stacked with the first photoactive layer. The term "closely stacked" means direct deposition, for example, the first photoactive layer is directly deposited on the anode layer.

[0132] In one embodiment, there are two methods for preparing the first photoactive layer:

[0133] One method is to add a polymer donor material and an anode buffer layer material containing an anchoring group into an organic solvent to prepare a first photoactive layer solution, and then prepare the first photoactive layer by a printing or coating method;

[0134] Another method is to dissolve the polymer donor material solvent in a first organic solvent, dissolve the anode buffer layer material containing the anchoring group in a second organic solvent, and then form a first photoactive layer solution by blending, and then prepare the first photoactive layer by printing or coating.

[0135] The printing or coating preparation method can be, but is not limited to, inkjet printing, spray printing, screen printing, dip coating, spin coating, blade coating, roller printing, twist roller printing, lithography, flexographic printing, rotary printing, spray coating, brush coating, pad printing, slot extrusion coating, etc. Slot coating, spin coating, blade coating, and inkjet printing are preferred.

[0136] The organic solvent, the first organic solvent, and the second organic solvent are independently selected from dichloromethane, chloroform, chlorobenzene, chloroform, o-dichlorobenzene, tetrahydrofuran, anisole, 2,4-dimethylanisole, 1-methylnaphthalene, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1,4-dioxane, acetone, methyl ethyl ketone, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, ethyl acetate, n-butyl acetate, N,N-dimethylformamide, dimethylacetamide, dimethyl sulfoxide, 1,5-dimethyltetrahydrofuran, acetophenone, tetralin, 2-methylthiophene, 3-methylthiophene, decalin, indane, methyl benzoate, ethyl benzoate, mesitylene, or a mixture of the above solvents.

[0137] In one embodiment, the organic solvent is preferably selected from chlorobenzene, toluene, o-xylene, 3-methylthiophene or chloroform, but is not limited thereto.

[0138] In one embodiment, the first organic solvent is preferably selected from chlorobenzene, toluene, o-xylene, 3-methylthiophene or chloroform, but not limited thereto; further, the second organic solvent is selected from tetrahydrofuran, but not limited thereto.

[0139] In one embodiment, the thickness of the first photoactive layer is in the range of 1-20 nm; preferably, the thickness of the first photoactive layer is in the range of 1-10 nm.

[0140] In one embodiment, according to the organic solar cell device of the present invention, the second photoactive layer comprises a photoactive layer donor material and a photoactive layer acceptor material.

[0141] In one embodiment, the photoactive layer donor material in the second photoactive layer is selected from one or more polymers P B .

[0142] Furthermore, the polymer P B Selected from the following structures:

[0143]

[0144] Among them: Ar5, Ar6, R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 , n have the same meaning as described above.

[0145] Furthermore, the polymer P B Selected from the following structures:

[0146]

[0147] Where: R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 , R 108 , R 109 , R 110 , R 111 , R 112 , R 113 , R 114 , R 115 , R 116 , W1, and n have the same meanings as described above.

[0148] In a specific embodiment, the photoactive layer donor material in the second photoactive layer is selected from one, two or more of polymers (P-1)-(P-18), but is not limited thereto.

[0149] In a preferred embodiment, the polymer P in the first photoactive layer A The photoactive layer donor material in the second photoactive layer is selected from the same material. For example, if the photoactive layer donor material in the second photoactive layer is selected from (P-1), then the polymer P in the first photoactive layer is A Also selected from (P-1).

[0150] In one embodiment, the photoactive layer acceptor material in the second photoactive layer is selected from a non-fullerene acceptor material or a fullerene derivative acceptor material.

[0151] The non-fullerene acceptor material is preferably a small molecule non-fullerene acceptor material or a polymer non-fullerene acceptor material.

[0152] Preferably, the small molecule non-fullerene acceptor material is selected from the Y series non-fullerene acceptor materials based on the A-DA'DA structure, wherein A represents an electron-withdrawing end group and DA'D represents a Y series large condensed ring core.

[0153] Preferably, the polymer non-fullerene acceptor material is selected from Where: π is the connection unit.

[0154] Furthermore, the non-fullerene acceptor material is selected from the structure described in formula (V-1) or formula (V-2):

[0155]

[0156] Where: R 200 , R 201 , R 202 , R 203 , R204 , R 205 , R 206 , R 207 , R 208 , R 209 Each occurrence is independently selected from -H (hydrogen), -D (deuterium), -F, -Cl, -Br, -I, cyano, straight-chain alkyl having 1-20 carbon atoms, straight-chain alkoxy having 1-20 carbon atoms, straight-chain alkylthio having 1-20 carbon atoms, straight-chain alkoxycarboxyl having 1-20 carbon atoms, branched or cyclic alkyl having 3-20 carbon atoms, branched or cyclic alkoxy having 3-20 carbon atoms, branched or cyclic alkylthio having 3-20 carbon atoms, branched alkoxycarboxyl having 3-20 carbon atoms, aromatic groups having 6-20 carbon atoms, heteroaromatic groups having 5-20 ring atoms, or groups formed by combinations of these groups;

[0157] n is the number of repeating units, and n is selected from integers greater than 1.

[0158] In one embodiment, R 200 , R 201 , R 202 , R 203 Each occurrence is independently selected from -H (hydrogen), -D (deuterium), a straight-chain alkyl group having 1 to 16 carbon atoms, a straight-chain alkoxy group having 1 to 16 carbon atoms, a straight-chain alkylthio group having 1 to 16 carbon atoms, a branched or cyclic alkyl group having 3 to 16 carbon atoms, a branched or cyclic alkoxy group having 3 to 16 carbon atoms, a branched or cyclic alkylthio group having 3 to 16 carbon atoms, a phenyl group, a thienyl group, a thienothiphenyl group, or a group formed by a combination of these groups.

[0159] Furthermore, R 200 , R 201 Each occurrence is independently selected from -H (hydrogen), -D (deuterium), a straight-chain alkyl group having 1-16 carbon atoms, a straight-chain alkoxy group having 1-16 carbon atoms, a straight-chain alkylthio group having 1-16 carbon atoms, a branched-chain alkyl group having 3-16 carbon atoms, a branched-chain alkoxy group having 3-16 carbon atoms, a branched-chain alkylthio group having 3-16 carbon atoms, a phenyl group, a thienyl group, or a group formed by combining a phenyl group with a branched-chain alkyl group having 3-16 carbon atoms, or a group formed by combining a thienyl group with a branched-chain alkyl group having 3-16 carbon atoms.

[0160] Furthermore, R 202 , R 203 Each occurrence is independently selected from -H (hydrogen), -D (deuterium), a straight chain alkyl having 1-16 carbon atoms, or a branched chain alkyl having 3-16 carbon atoms.

[0161] In one embodiment, R204 , R 205 , R 206 , R 207 , R 208 Each occurrence is independently selected from -H (hydrogen), -D (deuterium), -F, -Cl, -Br, -I, cyano, -CF3, straight chain or branched alkyl having 1 to 10 carbon atoms.

[0162] In one embodiment, R 209 Each occurrence is independently selected from -H (hydrogen), -D (deuterium), -F, -Cl, -Br, -I, cyano, straight-chain alkyl having 1-10 carbon atoms, straight-chain alkoxy having 1-10 carbon atoms, straight-chain alkylthio having 1-10 carbon atoms, straight-chain alkoxycarboxyl having 1-10 carbon atoms, branched or cyclic alkyl having 3-10 carbon atoms, branched or cyclic alkoxy having 3-10 carbon atoms, branched or cyclic alkylthio having 3-10 carbon atoms, branched alkoxycarboxyl having 3-10 carbon atoms, or a group formed by a combination of these groups.

[0163] In a specific embodiment, the non-fullerene acceptor material is selected from one, two or more of the following structures:

[0164]

[0165]

[0166] The fullerene derivative acceptor material is selected from C60 derivatives or C70 derivatives, and the fullerene derivative acceptor material includes but is not limited to: one, two or three or more of PC61BM ([6,6]-phenyl C61 butyric acid methyl ester), PC71BM ([6,6]-phenyl C71 butyric acid methyl ester), indene-containing fullerene, etc.

[0167] Preferably, the mass ratio of the active layer donor material to the active layer acceptor material in the second photoactive layer is 0.8:1.8 to 1.8:0.8; further, the mass ratio of the active layer donor material to the active layer acceptor material is 1:1 to 1:1.8; further, the mass ratio is 1:1 to 1:1.5; further, the mass ratio is 1:1 to 1:1.2.

[0168] The second photoactive layer may be formed by dissolving a photoactive material in an organic solvent and then coating the resulting solution by methods such as spin coating, dip coating, screen printing, gravure printing, spray coating, doctor blade, slit coating, and inkjet printing, but is not limited thereto.

[0169] The organic solvent is selected from dichloromethane, chloroform, chlorobenzene, chloroform, o-dichlorobenzene, tetrahydrofuran, anisole, 2,4-dimethylanisole, 1-methylnaphthalene, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1,4-dioxane, acetone, methyl ethyl ketone, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, ethyl acetate, n-butyl acetate, N,N-dimethylformamide, dimethylacetamide, dimethyl sulfoxide 1,5-dimethyltetrahydrofuran, acetophenone, tetralin, 2-methylthiophene, 3-methylthiophene, decalin, indane, methyl benzoate, ethyl benzoate, mesitylene or a mixture of the above solvents.

[0170] In one embodiment, the thickness of the second photoactive layer is selected from 50-400 nm; preferably, the thickness is selected from 100-300 nm.

[0171] In one embodiment, the material used to prepare the cathode and the anode can be selected from metals, such as vanadium (V), chromium (Cr), zinc (Zn), silver (Ag), aluminum (Al), platinum (Pt), tungsten (W), copper (Cu), molybdenum (Mo), gold (Au), nickel (Ni), palladium (Pd), or alloys of the above metals; conductive nanomaterials, such as metal nanowires, nanoparticle slurries, graphene, carbon nanotubes, etc.; metal oxides, such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), etc.; combinations of metals and oxides, such as ZnO:Al or SnO2:Sb, etc.; and conductive polymers, such as PEDOT:PSS, polypyrrole and polyaniline, etc.; or materials with a multilayer structure, such as LiF / Al, LiO2 / Al, LiF / Fe, MoO3 / Al, Al:Li, Al:BaF2 and Al:BaF2:Ba, etc., but are not limited thereto.

[0172] In one embodiment, the organic solar cell device according to the present invention further comprises a cathode buffer layer, wherein the cathode buffer layer is located between the cathode and the second photoactive layer.

[0173] In a preferred embodiment, the cathode buffer layer material is selected from metal oxides or polymers. The metal oxide can be a metal complex containing 8-hydroxyquinoline, a complex containing Alq3, a metal complex containing Liq, LiF, Ca, titanium oxide (TiO x ), zinc oxide (ZnO), cesium carbonate (Cs2CO3), etc. The polymer can be PFN-Br or PFN or PDINN or PDINO or PNDIT-F3N-Br or PNDIT-F3N, etc., but is not limited thereto.

[0174] It should be noted that, in order to improve the performance of the organic solar cell device, the functional layer may further include other functional layers, including but not limited to a charge blocking layer.

[0175] In one embodiment, the organic solar cell device according to the present invention comprises an anode, a first photoactive layer, a second photoactive layer, a cathode buffer layer and a cathode stacked sequentially from bottom to top.

[0176] In one embodiment, the organic solar cell further comprises a substrate. Specifically, the substrate may be disposed on one side of the anode and on a different side from the photoactive layer.

[0177] In another embodiment, the organic solar cell further comprises a substrate. Specifically, the substrate can be disposed on one side of the cathode and on a different side from the photoactive layer.

[0178] Specifically, the substrate can use a substrate with excellent transparency, surface smoothness, ease of operation and water resistance. For example, a glass substrate, a thin film glass substrate or a transparent plastic substrate can be used. The plastic substrate may include a film in a single or multilayer form, such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyetheretherketone (PEEK) and polyimide (PI), but is not limited thereto, and substrates commonly used for organic solar cells may also be used.

[0179] The organic solar cell device according to the present invention can be applied to wearable devices, smart Internet of Things, smart homes, smart agriculture, building photovoltaics, vehicle-mounted photovoltaics and other fields.

[0180] The present invention further relates to a mixture, said mixture consisting of a polymer donor material P A and an anode buffer layer material containing an anchoring group, wherein the polymer donor material (P A ) and the description of the anode buffer layer material containing anchoring groups are the same as described above.

[0181] The invention further relates to a composition comprising a mixture as described above and at least one organic solvent.

[0182] The organic solvent is selected from dichloromethane, chloroform, chlorobenzene, chloroform, o-dichlorobenzene, tetrahydrofuran, anisole, 2,4-dimethylanisole, 1-methylnaphthalene, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1,4-dioxane, acetone, methyl ethyl ketone, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, ethyl acetate, n-butyl acetate, N,N-dimethylformamide, dimethylacetamide, dimethyl sulfoxide 1,5-dimethyltetrahydrofuran, acetophenone, tetralin, 2-methylthiophene, 3-methylthiophene, decalin, indane, methyl benzoate, ethyl benzoate, mesitylene or a mixture of the above solvents.

[0183] Compared with the prior art, the present invention has the following significant advantages:

[0184] 1. The organic solar cell device disclosed in the present invention comprises a first photoactive layer and a second photoactive layer, wherein the first photoactive layer comprises an anode buffer layer material (SAMs) comprising an anchoring group and a polymer donor material, and the second photoactive layer comprises a photoactive layer donor material and an acceptor material. Compared with conventional organic solar cell devices, the device exhibits excellent photoelectric conversion performance because:

[0185] First, during the preparation of the first photoactive layer, SAMs can be induced to form a single-molecule SAM layer by in-situ deposition through chemical bonding. The blending of polymer donor materials and SAMs can assist in limiting the spatial position of SAMs, so that SAMs form a more uniform film during in-situ deposition.

[0186] Second, the presence of the polymer donor in the first photoactive layer can induce the donor material in the second photoactive layer to aggregate toward the first photoactive layer (due to the effect of molecular surface energy), so that the concentration of the donor material is higher near the first photoactive layer, and the concentration of the acceptor material is higher near the cathode buffer layer. By utilizing this spontaneously formed inherent vertical phase distribution, the second active layer has a better morphology distribution, which can effectively improve the dissociation and transfer of charges, thereby improving the photoelectric performance of the device.

[0187] Third, the device structure protected by the present invention also has performance advantages when preparing large-area organic solar cell devices. The reason is that when the anode buffer layer material containing anchoring groups is used as a single component in the anode buffer layer, the anode buffer layer based on SAMs is usually very thin, which makes it difficult to form a uniform and stable thin film during preparation, thereby causing the photoelectric performance of the organic solar cell device to deteriorate. The organic solar cell device described in the present invention effectively solves the SAM film formation problem. BRIEF DESCRIPTION OF THE DRAWINGS

[0188] Figure 1It is a schematic diagram of the structures of device embodiments 1-12 and large-area organic solar cell device embodiment 1 of the present invention.

[0189] Figure 2 It is a schematic diagram of the structures of comparative examples 1-10 of the device of the present invention and comparative example 1 of a large-area organic solar cell device. DETAILED DESCRIPTION

[0190] The present invention will be described below in conjunction with preferred embodiments, but the present invention is not limited to the following embodiments. It should be understood that the attached claims summarize the scope of the present invention. Under the guidance of the concept of the present invention, those skilled in the art should be aware that certain changes made to the various embodiments of the present invention will be covered by the spirit and scope of the claims of the present invention.

[0191] In order to make the purpose, technical scheme and effect of the present invention clearer and more specific, the present invention is further described in detail below. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention. Based on the described embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0192] The terms "and / or", "or / and", and "and / or" used herein include any one of two or more related listed items, and also include any and all combinations of related listed items, wherein the any and all combinations include any combination of two related listed items, any more related listed items, or all related listed items. It should be noted that when at least three items are connected by at least two conjunctions selected from "and / or", "or / and", and "and / or", it should be understood that in the present invention, the technical solution undoubtedly includes technical solutions connected by "logical and", and undoubtedly includes technical solutions connected by "logical or". For example, "A and / or B" includes three parallel solutions of A, B and A+B. For example, the technical solution of "A, and / or, B, and / or, C, and / or, D" includes any one of A, B, C, and D (that is, the technical solution that is all connected by "logical OR"), and also includes any and all combinations of A, B, C, and D, that is, the combination of any two or any three of A, B, C, and D, and also includes the combination of four of A, B, C, and D (that is, the technical solution that is all connected by "logical AND").

[0193] In the present invention, organic photovoltaic device, organic solar cell and OPV have the same meaning and can be interchangeable.

[0194] In the present invention, active layer and photoactive layer have the same meaning and can be interchanged.

[0195] In the present invention, "substituted" means that one or more hydrogen atoms in the defined group are replaced by a substituent. For example, a phenyl group substituted by one R means that one hydrogen atom on the phenyl group is replaced by R.

[0196] In the present invention, the "number of ring atoms" refers to the number of atoms constituting the ring itself of a structural compound (e.g., a monocyclic compound, a condensed ring compound, a cross-linked compound, a carbocyclic compound, a heterocyclic compound) in which atoms are bonded to form a ring. When the ring is substituted by a substituent, the atoms contained in the substituent are not included in the ring atoms. The same applies to the "number of ring atoms" described below unless otherwise specified. In an aromatic group, the number of ring atoms is the same as the number of carbon atoms; in a heteroaromatic group, the number of ring atoms is the number of carbon atoms plus the number of heteroatoms; for example, the number of ring atoms of a benzene ring is 6, the number of ring atoms of a naphthalene ring is 10, the number of ring atoms of a quinoline ring is 10, the number of ring atoms of a thienyl group is 5, the number of ring atoms of a pyridine ring is 6, and the number of ring atoms of a thienothiophene group is 8.

[0197] In the present invention, "aromatic group" refers to an optional functional group or substituent derived from an aromatic carbocyclic ring. The aromatic group can be a monocyclic aromatic group (such as phenyl) or a polycyclic aromatic group. In other words, the aromatic group can be a monocyclic aromatic group, a condensed aromatic group, two or more monocyclic aromatic groups conjugated by carbon-carbon bonds, monocyclic aromatic groups and condensed aromatic groups conjugated by carbon-carbon bonds, and two or more condensed aromatic groups conjugated by carbon-carbon bonds. That is, unless otherwise specified, two or more aromatic groups conjugated by carbon-carbon bonds can also be regarded as aromatic groups of the present invention. Preferably, the "aromatic group" is selected from aromatic groups having 6-30 C atoms; further, selected from aromatic groups having 6-20 C atoms; further, selected from aromatic groups having 6-10 C atoms; aromatic groups include but are not limited to: phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, fluoranthenyl, triphenylene, pyrenyl, perylene, naphthyl, fluorenyl, perylene, acenaphthene and derivatives thereof.

[0198] In the present invention, "heteroaromatic group" refers to a monovalent heteroaromatic ring or a derivative thereof containing 1, 2, 3, 4, 5, 6 or more heteroatoms in the ring, and the heteroatom may be at least one of B, O, N, P, Si, Se and S. The heteroaromatic group may be a monocyclic heteroaromatic group or a polycyclic heteroaromatic group. In other words, the heteroaromatic group may be a single heteroaromatic ring system or a plurality of heteroaromatic ring systems conjugated by carbon-carbon bonds, and any heteroaromatic ring system is a heteroaromatic monocyclic ring or a heteroaromatic condensed ring. Preferably, the "heteroaromatic group" is selected from heteroaromatic groups having 5-30 ring atoms; further, selected from heteroaromatic groups having 5-20 ring atoms; further, selected from heteroaromatic groups having 5-10 ring atoms. Heteroaromatic groups include, but are not limited to, thienyl, furanyl, pyrrolyl, oxadiazolyl, triazolyl, imidazolyl, pyridyl, bipyridyl, pyrimidinyl, triazine, acridinyl, pyridazinyl, pyrazinyl, quinolyl, thienothiphenyl, and the like and their derivatives.

[0199] In the present invention, the carbon number of the straight chain alkyl group can be 1 to 20, 1 to 16, 1 to 10, or 1 to 6; non-limiting examples of the straight chain alkyl group include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, -C 10 H 21 , -C 11 H 23 , -C 12 H 25 , -C 13 H 27 , -C 14 H 29 , -C 15 H 31 , -C 16 H 33 ;

[0200] In the present invention, the number of carbon atoms of the branched alkyl group may be 3 to 20, 3 to 16, 3 to 10, or 3 to 6; non-limiting examples of the branched alkyl group include: isopropyl, a branched alkyl group containing 4 C atoms, a branched alkyl group containing 5 C atoms, a branched alkyl group containing 6 C atoms, a branched alkyl group containing 7 C atoms, a branched alkyl group containing 8 C atoms, a branched alkyl group containing 9 C atoms, a branched alkyl group containing 10 C atoms, a branched alkyl group containing 11 C atoms, a branched alkyl group containing 12 C atoms, a branched alkyl group containing 13 C atoms, a branched alkyl group containing 14 C atoms, a branched alkyl group containing 15 C atoms, and a branched alkyl group containing 16 C atoms.

[0201] In the present invention, the number of carbon atoms of the cyclic alkyl group may be 3 to 20, 3 to 16, 3 to 10, or 3 to 6; non-limiting examples of the cyclic alkyl group include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, a cyclic alkyl group containing 7 C atoms, a cyclic alkyl group containing 8 C atoms, a cyclic alkyl group containing 9 C atoms, a cyclic alkyl group containing 10 C atoms, a cyclic alkyl group containing 11 C atoms, a cyclic alkyl group containing 12 C atoms, a cyclic alkyl group containing 13 C atoms, a cyclic alkyl group containing 14 C atoms, a cyclic alkyl group containing 15 C atoms, and a cyclic alkyl group containing 16 C atoms.

[0202] The term "straight chain alkoxy" refers to a group having the structure "-O-straight chain alkyl", and the straight chain alkyl is as defined above. The term "branched chain alkoxy" refers to a group having the structure "-O-branched chain alkyl", and the branched chain alkyl is as defined above. The term "cyclic alkoxy" refers to a group having the structure "-O-cyclic alkyl", and the cyclic alkyl is as defined above.

[0203] The term "straight-chain alkylthio" refers to a group having the structure "-S-straight-chain alkyl", wherein the straight-chain alkyl is as defined above. The term "branched-chain alkylthio" refers to a "-S-branched-chain alkyl", wherein the branched-chain alkyl is as defined above. The term "cyclic alkylthio" refers to a "-S-cyclic alkyl", wherein the cyclic alkyl is as defined above.

[0204] The term "straight chain ester group" refers to a group having the structure "-COO-straight chain alkyl", wherein the straight chain alkyl is as defined above. The term "branched chain ester group" refers to a group having the structure "-COO-branched chain alkyl", wherein the branched chain alkyl is as defined above.

[0205] In the present invention, multiple substituent substitution refers to the range including double substitution up to the maximum available substitution. When the group mentioned in the present invention is substituted by one or more substituents, it means that the substituent can exist at one or more available substitution positions on its connecting group. When the substituent exists at multiple available substitution positions, the substituents can be of the same structure or different structures.

[0206] In the present specification, when the position of a substituent on a group is not fixed, it means that any connectable site in the group can serve as a connecting site.

[0207] like Can be expressed

[0208] In the present invention, one or more groups "independently selected from" means that when one or more groups appear simultaneously and in multiple places in a compound, they are all independently selected and may be the same or different.

[0209] The "combinations thereof", "any combinations thereof", "any combinations thereof", "combinations" and the like used in the present invention include all suitable combinations of any two, three or four or more of the listed groups.

[0210] In the present invention, “further”, “furthermore”, “particularly”, etc. are used for descriptive purposes to indicate differences in content, but should not be construed as limiting the scope of protection of the present invention.

[0211] In the present invention, "optionally", "optional", and "optional" mean optional, that is, any one of the two parallel solutions of "yes" or "no". If multiple "options" appear in a technical solution, unless otherwise specified and there is no contradiction or mutual restriction, each "optional" is independent.

[0212] In the process of describing the structural elements of the present invention, the words "include" or "comprises" and the like used in the present invention mean that the devices or materials appearing before the word include the devices or materials listed after the word and their equivalents, but do not exclude other devices or materials.

[0213] In the description of the present invention, it should be understood that the terms "upper", "lower", "between layers", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the accompanying drawings, or are the orientations or positional relationships in which the organic solar cell device is conventionally placed when in use, or are the orientations or positional relationships conventionally understood by those skilled in the art. These are only for the convenience of describing the present invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be understood as a limitation on the present invention.

[0214] Preparation and characterization of small-area organic solar cell (OPV) devices (device area: 0.06 cm 2 )

[0215] Device Example 1:

[0216] 1) ITO substrate cleaning:

[0217] The ITO conductive glass was cleaned with detergent, rinsed, and then ultrasonically cleaned with deionized water, acetone, and isopropanol for 15 minutes, then blown dry with nitrogen and treated in a plasma cleaner for 5 minutes to further clean the surface and improve wettability.

[0218] 2) Preparation of the first photoactive layer

[0219] In a glove box (inert gas atmosphere), the anode buffer layer material (HTM-1) containing an anchoring group was dissolved in tetrahydrofuran to form a solution 1 of 1 mg / mL, and the polymer donor material (P-2) was dissolved in o-xylene to form a solution 2 of 1 mg / mL. Then, solution 1 and solution 2 were blended in a volume ratio of 1:10 to obtain solution 3, and solution 3 was evenly spin-coated on ITO to obtain a first photoactive layer with a thickness of about 8 nm.

[0220] 3) Preparation of the second photoactive layer

[0221] In a glove box (inert gas atmosphere), the second photoactive layer solution was evenly spin-coated on the first photoactive layer at a rotation speed of 1800-4000 rpm to obtain a second photoactive layer with a total thickness of about 100 nm.

[0222] Among them, the donor material in the second photoactive layer material is selected from the polymer donor material (P-2), and the acceptor material is selected from the non-fullerene acceptor material (A-11), the mass ratio of the donor material to the acceptor material is 1:1.3, (P-2): (A-11) are dissolved in o-xylene to prepare a second photoactive layer solution, wherein the concentration of the polymer donor material (P-2) in o-xylene is 7 mg / mL.

[0223] 4) Preparation of cathode buffer layer

[0224] After thermal annealing on a hot plate at 100°C for 10 minutes, the cathode buffer layer material PDINN (PDINN was dissolved in methanol to prepare a solution with a concentration of 1 mg / mL) was evenly spin-coated on the second photoactive layer at a spin coating speed of 3000-4000 rpm to obtain a cathode buffer layer with a thickness of about 10 nm.

[0225] 5) Cathode layer preparation

[0226] In high vacuum (1×10- 6 Ag was evaporated onto the cathode buffer layer at 400 mbar to form a cathode layer with a thickness of about 100 nm.

[0227] 6) Packaging

[0228] The devices were encapsulated with UV-curable resin in a nitrogen glove box.

[0229] Device Example 2:

[0230] The preparation method of device example 2 is the same as that of device example 1, except that the anode buffer layer material containing anchoring groups in the first photoactive layer is different. The anode buffer layer material containing anchoring groups (HTM-1) is replaced by an anode buffer layer material containing anchoring groups (HTM-8).

[0231] Device Example 3:

[0232] The preparation method of device example 3 is the same as that of device example 1, except that the anode buffer layer material containing the anchoring group in the first photoactive layer is different. The anode buffer layer material containing the anchoring group (HTM-1) is replaced by the anode buffer layer material containing the anchoring group (HTM-11).

[0233] Device Example 4:

[0234] The preparation method of device example 4 is the same as that of device example 1, except that the anode buffer layer material containing the anchoring group in the first photoactive layer is different. The anode buffer layer material containing the anchoring group (HTM-1) is replaced by the anode buffer layer material containing the anchoring group (HTM-16).

[0235] Device Example 5:

[0236] The preparation method of device example 5 is the same as that of device example 1, except that the anode buffer layer material containing anchoring groups in the first photoactive layer is different. The anode buffer layer material containing anchoring groups (HTM-1) is replaced by an anode buffer layer material containing anchoring groups (HTM-42).

[0237] Device Example 6:

[0238] The preparation method of device example 6 is the same as that of device example 1, except that the anode buffer layer material containing the anchoring group in the first photoactive layer is different. The anode buffer layer material containing the anchoring group (HTM-1) is replaced by the anode buffer layer material containing the anchoring group (HTM-58).

[0239] Device Example 7:

[0240] The preparation method of device implementation 7 is the same as that of device implementation example 1, except that the anode buffer layer material containing the anchoring group in the first photoactive layer is different. The anode buffer layer material containing the anchoring group (HTM-1) is replaced by the anode buffer layer material containing the anchoring group (HTM-59).

[0241] Device Example 8:

[0242] The preparation method of device example 8 is the same as that of device example 1, except that the anode buffer layer material containing the anchoring group in the first photoactive layer is different. The anode buffer layer material containing the anchoring group (HTM-1) is replaced by the anode buffer layer material containing the anchoring group (HTM-67).

[0243] Device Comparative Example 1

[0244] 1) ITO substrate cleaning:

[0245] The ITO conductive glass was cleaned with detergent, rinsed, and then ultrasonically cleaned with deionized water, acetone, and isopropanol for 15 minutes, then blown dry with nitrogen and treated in a plasma cleaner for 5 minutes to further clean the surface and improve wettability.

[0246] 2) Anode buffer layer preparation

[0247] In a glove box (inert gas atmosphere), the anode buffer layer material (HTM-1) containing the anchoring group was dissolved in anhydrous ethanol to form a 0.3 mg / mL anode buffer layer solution, and then the anode buffer layer solution was spin-coated at a speed of 2500 rpm for 20 seconds to obtain an anode buffer layer.

[0248] 3) Preparation of photoactive layer

[0249] In a glove box (inert gas atmosphere), the photoactive layer solution was evenly spin-coated on the anode buffer layer at a rotation speed of 1800-4000 rpm to obtain a photoactive layer with a total thickness of about 100 nm.

[0250] Among them, the donor material in the photoactive layer material is selected from the polymer donor material (P-2), and the acceptor material is selected from the non-fullerene acceptor material (A-11). The mass ratio of the donor material to the acceptor material is 1:1.3. (P-2): (A-11) are dissolved in o-xylene to prepare a second photoactive layer solution, wherein the concentration of the polymer donor material (P-2) in o-xylene is 7 mg / mL.

[0251] 4) Preparation of cathode buffer layer

[0252] After thermal annealing on a hot plate at 100°C for 10 minutes, the cathode buffer layer material PDINN (PDINN was dissolved in methanol to prepare a solution with a concentration of 1 mg / mL) was evenly spin-coated on the photoactive layer at a spin coating speed of 3000-4000 rpm to obtain a cathode buffer layer with a thickness of about 10 nm.

[0253] 5) Cathode layer preparation

[0254] In high vacuum (1×10 -6 Ag was evaporated onto the cathode buffer layer at 400 mbar to form a cathode layer with a thickness of about 100 nm.

[0255] 6) Packaging

[0256] The devices were encapsulated with UV-curable resin in a nitrogen glove box.

[0257] Device Comparative Example 2

[0258] The preparation method of device comparison example 2 is the same as that of device comparison example 1, except that the anode buffer layer material in the anode buffer layer is different, and the anode buffer layer material containing an anchoring group (HTM-1) is replaced by an anode buffer layer material containing an anchoring group (HTM-8).

[0259] Device Comparative Example 3

[0260] The preparation method of device comparison example 3 is the same as that of device comparison example 1, except that the anode buffer layer material in the anode buffer layer is different, and the anode buffer layer material containing an anchoring group (HTM-1) is replaced by an anode buffer layer material containing an anchoring group (HTM-11).

[0261] Device Comparative Example 4

[0262] The preparation method of device comparison example 4 is the same as that of device comparison example 1, except that the anode buffer layer material in the anode buffer layer is different, and the anode buffer layer material containing an anchoring group (HTM-1) is replaced by an anode buffer layer material containing an anchoring group (HTM-16).

[0263] Device Comparative Example 5

[0264] The preparation method of device comparison example 5 is the same as that of device comparison example 1, except that the anode buffer layer material in the anode buffer layer is different, and the anode buffer layer material containing an anchoring group (HTM-1) is replaced by an anode buffer layer material containing an anchoring group (HTM-42).

[0265] Device Comparative Example 6

[0266] The preparation method of device comparison example 6 is the same as that of device comparison example 1, except that the anode buffer layer material in the anode buffer layer is different, and the anode buffer layer material containing an anchor group (HTM-1) is replaced by an anode buffer layer material containing an anchor group (HTM-58).

[0267] Device Comparative Example 7

[0268] The preparation method of device comparison example 7 is the same as that of device comparison example 1, except that the anode buffer layer material in the anode buffer layer is different, and the anode buffer layer material containing an anchor group (HTM-1) is replaced by an anode buffer layer material containing an anchor group (HTM-59).

[0269] Device Comparative Example 8

[0270] The preparation method of device comparison example 8 is the same as that of device comparison example 1, except that the anode buffer layer material in the anode buffer layer is different, and the anode buffer layer material containing an anchor group (HTM-1) is replaced by an anode buffer layer material containing an anchor group (HTM-67).

[0271] The prepared organic solar cell device was subjected to a performance test. Under the irradiation of the AM1.5 standard light of a solar simulator, the current-voltage curve of the cell was tested and the photoelectric conversion efficiency was calculated. The specific values ​​are shown in Table 1-8:

[0272] Table 1

[0273]

[0274] Table 2

[0275]

[0276] Table 3

[0277]

[0278] Table 4

[0279]

[0280] Table 5

[0281]

[0282] Table 6

[0283]

[0284] Table 7

[0285]

[0286] Table 8

[0287]

[0288] It can be seen from the data in Tables 1-8 that the photoelectric conversion efficiency of the organic solar cell device according to the present invention is greatly improved compared with the device comparison example. The reason is that the structure of the organic solar cell device according to the present invention is more optimized, and the dissociation and transmission of charges are more efficient.

[0289] Device Example 9:

[0290] 1) ITO substrate cleaning:

[0291] The ITO conductive glass was cleaned with detergent, rinsed, and then ultrasonically cleaned with deionized water, acetone, and isopropanol for 15 minutes, then blown dry with nitrogen and treated in a plasma cleaner for 5 minutes to further clean the surface and improve wettability.

[0292] 2) Preparation of the first photoactive layer

[0293] In a glove box (inert gas atmosphere), the anode buffer layer material (HTM-12) containing an anchoring group was dissolved in tetrahydrofuran to form a 1 mg / mL solution 1, and the polymer donor material (P-18) was dissolved in o-xylene to form a 1 mg / mL solution 2. Then, solution 1 and solution 2 were blended in a volume ratio of 1:10 to obtain solution 3, and solution 3 was evenly spin-coated on ITO to obtain a first photoactive layer with a thickness of about 8 nm.

[0294] 3) Preparation of the second photoactive layer

[0295] In a glove box (inert gas atmosphere), the second photoactive layer material solution (at a rotation speed of 1800-4000 rpm) is evenly spin-coated on the first photoactive layer to obtain an active material layer with a total thickness of about 100 nm.

[0296] Among them, the donor material in the second photoactive layer material is selected from the polymer donor material (P-18), and the acceptor material is selected from the non-fullerene acceptor material (A-20). The mass ratio of the donor material to the acceptor material is 1:1.2. (P-18): (A-20) are dissolved in o-xylene to prepare a second photoactive layer solution, wherein the total concentration of the polymer donor material (P-18) and the non-fullerene acceptor material (A-20) in o-xylene is 18 mg / mL.

[0297] 4) Preparation of cathode buffer layer

[0298] After thermal annealing on a hot plate at 100°C for 10 minutes, the cathode buffer layer material PDINO (PDINO was dissolved in methanol to prepare a solution with a concentration of 1 mg / mL) was evenly spin-coated on the active layer at a spin coating speed of 3000-4000 rpm to obtain a cathode buffer layer with a thickness of about 10 nm.

[0299] 5) Cathode layer preparation

[0300] In high vacuum (1×10 -6 Ag was evaporated onto the cathode buffer layer at 400 mbar to form a cathode layer with a thickness of 100 nm.

[0301] 6) Packaging

[0302] The devices were encapsulated with UV-curable resin in a nitrogen glove box.

[0303] Device Example 10:

[0304] The preparation method of device example 10 is the same as that of device example 9, except that the anode buffer layer material containing anchoring groups in the first photoactive layer is different. The anode buffer layer material containing anchoring groups (HTM-12) is replaced by the anode buffer layer material containing anchoring groups (HTM-64).

[0305] Device Comparative Example 9

[0306] 1) ITO substrate cleaning:

[0307] The ITO conductive glass was cleaned with detergent, rinsed, and then ultrasonically cleaned with deionized water, acetone, and isopropanol for 15 minutes, then blown dry with nitrogen and treated in a plasma cleaner for 5 minutes to further clean the surface and improve wettability.

[0308] 2) Anode buffer layer preparation

[0309] In a glove box (inert gas atmosphere), the anode buffer layer material (HTM-12) containing the anchoring group was dissolved in anhydrous ethanol to form a 0.3 mg / mL anode buffer layer solution, and then the anode buffer layer solution was spin-coated at a speed of 2500 rpm for 20 seconds to obtain an anode buffer layer.

[0310] 3) Preparation of photoactive layer

[0311] In a glove box (inert gas atmosphere), the photoactive layer solution was evenly spin-coated on the anode buffer layer at a rotation speed of 1800-4000 rpm to obtain an active material layer with a total thickness of about 100 nm.

[0312] The donor material in the photoactive layer material is selected from a polymer donor material (P-18), and the acceptor material is selected from a non-fullerene acceptor material (A-20). The mass ratio of the donor material to the acceptor material is 1:1.2. (P-18): (A-20) are dissolved in o-xylene to prepare a photoactive layer solution, wherein the total concentration of the polymer donor material (P-18) and the non-fullerene acceptor material (A-20) in o-xylene is 18 mg / mL.

[0313] 4) Preparation of cathode buffer layer

[0314] After thermal annealing on a hot plate at 100°C for 10 minutes, the cathode buffer layer material PDINO (PDINN is dissolved in methanol to prepare a solution with a concentration of 1 mg / mL) is evenly spin-coated on the photoactive layer at a spin coating speed of 3000-4000 rpm to obtain a cathode buffer layer with a thickness of about 10 nm.

[0315] 5) Cathode layer preparation

[0316] Ag was evaporated onto the cathode buffer layer in a high vacuum (1×10 -6 mbar) to form a cathode layer with a thickness of about 100 nm.

[0317] 6) Packaging

[0318] The devices were encapsulated with UV-curable resin in a nitrogen glove box.

[0319] Device Comparative Example 10

[0320] The preparation method of device comparison example 10 is the same as that of device comparison example 9, except that the anode buffer layer material is different, and the anode buffer layer material containing an anchoring group (HTM-12) is replaced by the anode buffer layer material containing an anchoring group (HTM-64).

[0321] The prepared organic solar cell device was subjected to a performance test. Under the irradiation of the AM1.5 standard light of a solar simulator, the current-voltage curve of the cell was tested and the photoelectric conversion efficiency was calculated. The specific values ​​are shown in Table 9-10:

[0322]

[0323] Table 9

[0324]

[0325] Table 10

[0326]

[0327] Device Example 11:

[0328] 1) ITO substrate cleaning:

[0329] The ITO conductive glass was cleaned with detergent, rinsed, and then ultrasonically cleaned with deionized water, acetone, and isopropanol for 15 minutes, then blown dry with nitrogen and treated in a plasma cleaner for 5 minutes to further clean the surface and improve wettability.

[0330] 2) Preparation of the first photoactive layer

[0331] In a glove box (inert gas atmosphere), the anode buffer layer material (HTM-4) containing the anchoring group was dissolved in tetrahydrofuran to form a 1 mg / mL solution 1, and the polymer donor material (P-4) was dissolved in chlorobenzene to form a 1 mg / mL solution 2. Then, solution 1 and solution 2 were blended in a volume ratio of 1:10 to obtain solution 3. Solution 3 was evenly spin-coated on ITO to obtain a first photoactive layer with a thickness of about 8 nm.

[0332] 3) Preparation of the second photoactive layer

[0333] In a glove box (inert gas atmosphere), the second photoactive layer material (the total concentration of the second photoactive layer donor material and the photoactive layer acceptor material in chlorobenzene is 10 mg / mL) is evenly spin-coated on the first photoactive layer at a rotation speed of 1800-4000 rpm to obtain a second photoactive layer with a total thickness of about 100 nm. Among them, the donor material in the photoactive layer material is selected from the polymer donor material (P-4), the acceptor material is selected from the non-fullerene acceptor material (A-2), and the mass ratio of the donor material to the acceptor material is 1:1.5.

[0334] 4) Preparation of cathode buffer layer

[0335] After thermal annealing on a hot plate at 100°C for 10 minutes, the cathode buffer layer material PDINO (PDINO was dissolved in methanol to prepare a solution with a concentration of 1 mg / mL) was evenly spin-coated on the second active layer at a spin coating speed of 3000-4000 rpm to obtain a cathode buffer layer with a thickness of about 10 nm.

[0336] 5) Cathode layer preparation

[0337] In high vacuum (1×10 -6 Ag was evaporated onto the cathode buffer layer at 400 mbar to form a cathode layer with a thickness of about 100 nm.

[0338] 6) Packaging

[0339] The devices were encapsulated with UV-curable resin in a nitrogen glove box.

[0340] Device Example 12:

[0341] The preparation method of device example 12 is the same as that of device example 11, except that the anode buffer layer material containing the anchoring group in the first photoactive layer is different. The anode buffer layer material containing the anchoring group (HTM-4) is replaced by the anode buffer layer material containing the anchoring group (HTM-28).

[0342] Device Example 13:

[0343] The preparation method of device example 13 is the same as that of device example 11, except that the anode buffer layer material containing the anchoring group in the first photoactive layer is different. The anode buffer layer material containing the anchoring group (HTM-4) is replaced by the anode buffer layer material containing the anchoring group (HTM-53).

[0344] The prepared organic solar cell device was subjected to a performance test. Under the irradiation of the AM1.5 standard light of a solar simulator, the current-voltage curve of the cell was tested and the photoelectric conversion efficiency was calculated. The specific values ​​are shown in Table 11:

[0345] Table 11

[0346]

[0347] By comparing the device data in Tables 1 to 11, it can be seen that the organic solar cell device according to the present invention exhibits excellent photoelectric conversion performance in different systems. The reason is that:

[0348] First: During the preparation of the first photoactive layer, SAMs can be deposited in situ to form a single-molecule SAM layer. The blending of polymer donor materials and SAMs can limit the spatial position of SAMs, so that SAMs form a more uniform film during in situ deposition.

[0349] Second, the presence of the polymer donor in the first photoactive layer can induce the donor material in the second photoactive layer to aggregate toward the first photoactive layer (due to the effect of molecular surface energy), so that the concentration of the donor material is higher near the first photoactive layer, and the concentration of the acceptor material is higher near the cathode buffer layer. By utilizing this spontaneously formed inherent vertical phase distribution, the second active layer has a better morphology distribution, which can effectively improve the dissociation and transfer of charges, thereby improving the photoelectric performance of the device.

[0350] Preparation and characterization of large-area organic solar cells (OPV) (device area: 18.9 cm 2 )

[0351] Large-area organic solar cell device embodiment 1

[0352] 1) ITO substrate cleaning:

[0353] The ITO conductive glass was cleaned with detergent, rinsed, and then ultrasonically cleaned with deionized water, acetone, and isopropanol for 15 minutes, then blown dry with nitrogen and treated in a plasma cleaner for 5 minutes to further clean the surface and improve wettability.

[0354] 2) Preparation of the first photoactive layer

[0355] In the air, the anode buffer layer material (HTM-14) containing anchor groups and the polymer donor material (P-2) are dissolved in toluene to form a first photoactive layer solution, wherein: the concentration of the anode buffer layer material (HTM-14) containing anchor groups in toluene is 0.1 mg / mL, and the concentration of the polymer donor material (P-2) in toluene is 1 mg / mL. The first photoactive layer solution is evenly scraped on the ITO to obtain a first photoactive layer with a thickness of about 8 nm.

[0356] 3) Preparation of the second photoactive layer

[0357] The second photoactive layer solution was coated on the first photoactive layer by a doctor blade in air to obtain an active material layer with a total thickness of about 100 nm.

[0358] Preparation method of the second photoactive layer material:

[0359] The donor material of the second photoactive layer is selected from the polymer donor material (P-2), and the acceptor material is selected from the non-fullerene acceptor materials (A-13) and (A-11), wherein the mass ratio of (P-2):(A-13):(A-11) is selected from 1:0.75:0.65, and the polymer donor material (P-2) and the non-fullerene acceptor materials (A-13) and (A-11) are dissolved in the organic solvent toluene, wherein the concentration of the polymer donor material (P-2) in toluene is 7 mg / mL.

[0360] 4) Preparation of cathode buffer layer

[0361] After the coated second photoactive layer device was thermally annealed on a hot plate at 100°C for 10 minutes, the cathode buffer layer material PNDIT-F3N (PNDIT-F3N was dissolved in methanol to prepare a solution with a concentration of 1.5 mg / mL) was evenly coated on the active layer to obtain a cathode buffer layer with a thickness of about 10 nm.

[0362] 5) Cathode layer preparation

[0363] In high vacuum (1×10 -6 Ag was evaporated onto the cathode buffer layer at 400 mbar to form a cathode layer with a thickness of about 100 nm.

[0364] 6) Packaging

[0365] The devices were encapsulated with UV-curable resin in a nitrogen glove box.

[0366] Large-area organic solar cell device comparative example 1

[0367] 1) ITO substrate cleaning:

[0368] The ITO conductive glass was cleaned with detergent, rinsed, and then ultrasonically cleaned with deionized water, acetone, and isopropanol for 15 minutes, then blown dry with nitrogen and treated in a plasma cleaner for 5 minutes to further clean the surface and improve wettability.

[0369] 2) Anode buffer layer preparation

[0370] The anode buffer layer material (HTM-14) containing anchoring groups was dissolved in anhydrous ethanol in air to form a 1 mg / mL anode buffer layer solution, and then the anode buffer layer solution was evenly scraped on the ITO at a speed of 10 mm / s.

[0371] 3) Preparation of photoactive layer

[0372] The photoactive layer solution was coated on the anode buffer layer by a doctor blade in air to obtain an active material layer with a total thickness of about 100 nm.

[0373] Photoactive layer material preparation method:

[0374] The photoactive layer donor material is selected from the polymer donor material (P-2), and the acceptor material is selected from the non-fullerene acceptor materials (A-13) and (A-11), wherein the mass ratio of (P-2):(A-13):(A-11) is selected from 1:0.75:0.65. The polymer donor material (P-2) and the non-fullerene acceptor materials (A-13) and (A-11) are dissolved in the organic solvent toluene to obtain a photoactive layer solution, wherein the concentration of the polymer donor material (P-2) in toluene is 7 mg / mL.

[0375] 4) Preparation of cathode buffer layer

[0376] After the device with the photoactive layer coated was thermally annealed on a hot plate at 100°C for 10 minutes, the cathode buffer layer material PNDIT-F3N (PNDIT-F3N was dissolved in methanol to prepare a solution with a concentration of 1.5 mg / mL) was evenly coated on the photoactive layer to obtain a cathode buffer layer with a thickness of about 10 nm.

[0377] 5) Cathode layer preparation

[0378] In high vacuum (1×10 -6 Ag was evaporated onto the cathode buffer layer at 400 mbar to form a cathode layer with a thickness of about 100 nm.

[0379] 6) Packaging

[0380] The devices were encapsulated with UV-curable resin in a nitrogen glove box.

[0381] The performance of the prepared large-area organic solar cell device was tested. Under the irradiation of the AM1.5 standard light of the solar simulator, the current-voltage curve of the cell was tested and the photoelectric conversion efficiency was calculated. The specific values ​​are shown in Table 13:

[0382] Table 13

[0383]

[0384] It can be seen from the comparison of device performance data in Table 13 that the organic solar cell device according to the present invention also has performance advantages when preparing a large area. The reason why the large-area organic solar cell device has poor performance compared with Example 1 is that when the anode buffer layer material containing an anchoring group is used as a single component in the anode buffer layer, the anode buffer layer based on SAMs is usually very thin, which makes it difficult to form a uniform and stable thin film during preparation, thereby causing the photoelectric performance of the organic solar cell device to deteriorate.

[0385] Although the embodiments of the present invention have been shown and described above, it is to be understood that the above embodiments are exemplary and are not to be construed as limitations of the present invention. A person skilled in the art may change, modify, replace and vary the above embodiments within the scope of the present invention.

Claims

1. An organic solar cell device comprising a cathode, an anode, a first photoactive layer and a second photoactive layer located between the cathode and the anode, characterized in that: The first photoactive layer is located on the anode, and the second photoactive layer is located on the first photoactive layer; the first photoactive layer comprises a polymer P A and an anode buffer layer material containing an anchoring group, wherein the anchoring group is selected from any of the following groups: The polymer P A Selected from photoactive layer polymer donor materials.

2. The organic solar cell device according to claim 1, characterized in that: The anode buffer layer material containing the anchoring group is selected from the following general formula: Wherein: Ar1 is selected from an aromatic group having 6 to 30 carbon atoms which is substituted or unsubstituted by one or more R, or a heteroaromatic group having 6 to 30 ring atoms which is substituted or unsubstituted by one or more R; Each occurrence of L is independently selected from a straight-chain alkyl group having 1 to 20 C atoms, a straight-chain alkoxy group having 1 to 20 C atoms, a straight-chain alkylthio group having 1 to 20 C atoms, a branched-chain alkyl group having 3 to 20 C atoms, a branched-chain alkoxy group having 3 to 20 C atoms, a branched-chain alkylthio group having 3 to 20 C atoms, an aromatic group having 6 to 20 carbon atoms which is unsubstituted or substituted by one or more R, a heteroaromatic group having 5 to 20 ring atoms which is unsubstituted or substituted by one or more R, or a group formed by a combination of the above groups; Each occurrence of A is independently selected from the following groups: m is selected from 1, 2, 3 or 4; * indicates the attachment site; Each occurrence of R is independently selected from -D, -F, -Cl, -Br, -I, cyano, nitro, amino, straight-chain alkyl having 1 to 20 C atoms, straight-chain alkoxy having 1 to 20 C atoms, straight-chain alkylthio having 1 to 20 C atoms, branched-chain alkyl having 3 to 20 C atoms, branched-chain alkoxy having 3 to 20 C atoms, branched-chain alkylthio having 3 to 20 C atoms, aromatic groups having 6 to 20 carbon atoms, heteroaromatic groups having 5 to 20 ring atoms, or groups formed by combinations of the above groups.

3. The organic solar cell device according to claim 2, characterized in that: L at each occurrence is independently selected from -CH2-, -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH2-CH2-CH2-, -CH2-CH2-CH2-CH2-CH2-, -CH2-CH2-CH2-CH2-CH2-CH2-, -CH2-CH2-CH2-CH2-CH2-CH2-, -CH2-CH2-CH2-CH2-CH2-CH2-CH2-, -CH2-CH2-CH2-CH2-CH2-CH2-CH2-, -CH2-CH2-CH2-CH2-CH2-CH2-CH2-, CH2-CH2-CH2-CH2-CH2-CH2-, CH2-CH2-CH2-CH2-CH2-CH2-, CH2-CH2-CH2-CH2-CH2-, CH2-CH2-CH2-CH2-CH2-, CH2-CH2-CH2-CH2-CH2-, CH2-CH2-CH2-CH2-CH2-, CH2-CH2-CH2-CH2-CH2-, CH2- b Substituted phenyl, unsubstituted or replaced by R b substituted pyridyl, unsubstituted or replaced by R b Substituted pyrimidinyl, unsubstituted or replaced by R b Substituted triazine, unsubstituted or replaced by R b Substituted benzothiadiazolyl, unsubstituted or replaced by R b Substituted biphenyl, unsubstituted or replaced by R b Substituted phenyl biphenylthiadiazolyl, unsubstituted or replaced by R b Substituted phenylbiphenylthiadiazolylbiphenyl; R b Each occurrence is independently selected from -D, -F, -Cl, -Br, -I, cyano, nitro, -CF3, or a straight chain alkyl group having 1-6 C atoms, or a branched chain alkyl group having 3-6 C atoms.

4. The organic solar cell device according to claim 2, characterized in that: The Ar1 is selected from any of the following structures: in: Ar2, Ar3, Ar4 are independently selected from aromatic groups having 6 to 20 carbon atoms which are substituted or unsubstituted by one or more R, or heteroaromatic groups having 6 to 20 ring atoms which are substituted or unsubstituted by one or more R; Each occurrence is independently selected from absence, a single bond, Each occurrence is independently selected from a single bond, R1, R2, R3, each occurrence, is independently selected from -H, -D, a straight-chain alkyl group having 1 to 20 C atoms, a straight-chain alkoxy group having 1 to 20 C atoms, a straight-chain alkylthio group having 1 to 20 C atoms, a branched-chain alkyl group having 3 to 20 C atoms, a branched-chain alkoxy group having 3 to 20 C atoms, a branched-chain alkylthio group having 3 to 20 C atoms, an aromatic group having 6 to 20 carbon atoms, a heteroaromatic group having 5 to 20 ring atoms, or a group formed by a combination of the above groups; R2 and R3 may or may not form a ring with each other; It indicates the connection site between Ar1 and -LA.

5. The organic solar cell device according to claim 4, characterized in that: Ar2, Ar3, Ar4 are independently selected from any of the following groups: in: Each occurrence of X is independently selected from C, CR4 or N; R4 is independently selected at each occurrence from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, amino, straight-chain alkyl having 1 to 20 C atoms, straight-chain alkoxy having 1 to 20 C atoms, straight-chain alkylthio having 1 to 20 C atoms, branched-chain alkyl having 3 to 20 C atoms, branched-chain alkoxy having 3 to 20 C atoms, branched-chain alkylthio having 3 to 20 C atoms, aromatic groups having 6 to 20 carbon atoms, heteroaromatic groups having 5 to 20 ring atoms, or groups formed by combinations of the above groups; When X is a fusion site, X is selected from C.

6. The organic solar cell device according to claim 5, characterized in that: The Ar1 is selected from the following structures: Wherein: n1 is independently selected from 0, 1, 2, 3 or 4; n2 is independently selected from 0, 1, 2, 3, 4 or 5; n3 is independently selected from 0, 1, 2, 3, 4, 5 or 6; n4 is independently selected from 0, 1 or 2; Preferably, each occurrence of R4 is independently selected from -D, -F, -Cl, -Br, -I, cyano, nitro, -CF3, methyl, ethyl, isopropyl, tert-butyl, methoxy, ethoxy, methylthio, ethylthio, phenyl, diphenylamino, R f Substituted phenyl, R f Substituted diphenylamine; wherein R f Each occurrence is independently selected from -D, -F, -Cl, -Br, -I, cyano, nitro, -CF3, methyl, ethyl, isopropyl, tert-butyl, methoxy, ethoxy, methylthio, ethylthio or phenyl.

7. The organic solar cell device according to claim 1, characterized in that: The anode buffer layer material containing the anchoring group is selected from any of the following structural formulas:

8. The organic solar cell device according to claim 1, characterized in that: The polymer P A Select from any of the following structures: Wherein: Ar5, Ar6 each time appears, independently selected from one or more R x A substituted or unsubstituted aromatic group having 6 to 30 carbon atoms, replaced by one or more R x A substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms, substituted by one or more R x a substituted or unsubstituted non-aromatic heterocycle having 5 to 30 ring atoms; R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 Each occurrence is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1-20 carbon atoms, straight-chain alkoxy having 1-20 carbon atoms, straight-chain alkylthio having 1-20 carbon atoms, straight-chain ester having 1-20 carbon atoms, branched-chain alkyl having 3-20 carbon atoms, branched-chain alkoxy having 3-20 carbon atoms, branched-chain alkylthio having 3-20 carbon atoms, branched-chain ester having 3-20 carbon atoms, or a group formed by a combination of the above groups; The R x Each occurrence is independently selected from: -D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1-20 carbon atoms, straight-chain alkoxy having 1-20 carbon atoms, straight-chain alkylthio having 1-20 carbon atoms, straight-chain ester having 1-20 carbon atoms, branched-chain alkyl having 3-20 carbon atoms, branched-chain alkoxy having 3-20 carbon atoms, branched-chain alkylthio having 3-20 carbon atoms, branched-chain ester having 3-20 carbon atoms, aromatic having 6-20 carbon atoms, heteroaromatic having 5-20 ring atoms, or a combination thereof; n is the number of repeating units and is selected from integers greater than 1.

9. The organic solar cell device according to claim 8, characterized in that: The polymer P A Select from any of the following structures: R 108 Each occurrence is independently selected from a straight chain alkyl group having 1 to 20 carbon atoms, or a branched chain alkyl group having 3 to 20 carbon atoms; R 109 Each occurrence is independently selected from -H, -D, a straight chain alkyl group having 1 to 10 carbon atoms, or a branched chain alkyl group having 3 to 10 carbon atoms; R 110 Each occurrence is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1-20 carbon atoms, straight-chain alkoxy having 1-20 carbon atoms, straight-chain alkylthio having 1-20 carbon atoms, straight-chain ester having 1-20 carbon atoms, branched-chain alkyl having 3-20 carbon atoms, branched-chain alkoxy having 3-20 carbon atoms, branched-chain alkylthio having 3-20 carbon atoms, branched-chain ester having 3-20 carbon atoms, or a group formed by a combination of the above groups; W1 each occurrence is independently selected from O, S, Se; R 111 , R 112 , R 113 Each occurrence is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1-20 carbon atoms, straight-chain alkoxy having 1-20 carbon atoms, straight-chain alkylthio having 1-20 carbon atoms, straight-chain ester having 1-20 carbon atoms, branched-chain alkyl having 3-20 carbon atoms, branched-chain alkoxy having 3-20 carbon atoms, branched-chain alkylthio having 3-20 carbon atoms, branched-chain ester having 3-20 carbon atoms, or a group formed by a combination of the above groups; R 114 , R 115 , R 116 Each occurrence is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1-20 carbon atoms, straight-chain alkoxy having 1-20 carbon atoms, straight-chain alkylthio having 1-20 carbon atoms, straight-chain ester having 1-20 carbon atoms, branched-chain alkyl having 3-20 carbon atoms, branched-chain alkoxy having 3-20 carbon atoms, branched-chain alkylthio having 3-20 carbon atoms, branched-chain ester having 3-20 carbon atoms, unsubstituted or replaced by one or more R y Substituted aromatic groups having 6 to 10 carbon atoms, unsubstituted or replaced by one or more R y A substituted heteroaromatic group having 5 to 10 ring atoms, or a group formed by a combination of the above groups; The R y Each occurrence is independently selected from: -D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1-20 carbon atoms, straight-chain alkoxy having 1-20 carbon atoms, straight-chain alkylthio having 1-20 carbon atoms, straight-chain ester having 1-20 carbon atoms, branched-chain alkyl having 3-20 carbon atoms, branched-chain alkoxy having 3-20 carbon atoms, branched-chain alkylthio having 3-20 carbon atoms, branched-chain ester having 3-20 carbon atoms, or a group formed by a combination of the above groups.

10. The organic solar cell device according to claim 1, characterized in that: The polymer P A One, two or more selected from the following structural formulas:

11. The organic solar cell device according to claim 1, characterized in that: The polymer P A The mass ratio of the anchoring group-containing anode buffer layer material is selected from 1:1 to 200:1; preferably, the mass ratio is selected from 10:1 to 100:

1.

12. The organic solar cell device according to claim 1, characterized in that: The first photoactive layer is composed of polymer P A and an anode buffer layer material containing an anchoring group.

13. The organic solar cell device according to claim 1, characterized in that: The second photoactive layer comprises a photoactive layer donor material and a photoactive layer acceptor material, wherein: the photoactive layer donor material is selected from one or more polymers P B , the polymer P B Selected from the following structures: Wherein: Ar5, Ar6 each time appears, independently selected from one or more R x A substituted or unsubstituted aromatic group having 6 to 30 carbon atoms, replaced by one or more R x A substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms, substituted by one or more R x a substituted or unsubstituted non-aromatic heterocycle having 5 to 30 ring atoms; R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 Each occurrence is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1-20 carbon atoms, straight-chain alkoxy having 1-20 carbon atoms, straight-chain alkylthio having 1-20 carbon atoms, straight-chain ester having 1-20 carbon atoms, branched-chain alkyl having 3-20 carbon atoms, branched-chain alkoxy having 3-20 carbon atoms, branched-chain alkylthio having 3-20 carbon atoms, branched-chain ester having 3-20 carbon atoms, or a group formed by a combination of the above groups; The R x Each occurrence is independently selected from: -D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1-20 carbon atoms, straight-chain alkoxy having 1-20 carbon atoms, straight-chain alkylthio having 1-20 carbon atoms, straight-chain ester having 1-20 carbon atoms, branched-chain alkyl having 3-20 carbon atoms, branched-chain alkoxy having 3-20 carbon atoms, branched-chain alkylthio having 3-20 carbon atoms, branched-chain ester having 3-20 carbon atoms, aromatic having 6-20 carbon atoms, heteroaromatic having 5-20 ring atoms, or a combination thereof; n is the number of repeating units and is selected from integers greater than 1.

14. The organic solar cell device according to claim 13, characterized in that: The polymer P in the first photoactive layer A The photoactive layer donor material is selected from the same material as that in the second photoactive layer.

15. The organic solar cell device according to claim 13, characterized in that: The organic solar cell device further comprises a cathode buffer layer, wherein the cathode buffer layer is located between the cathode and the second photoactive layer.

16. A mixture, characterized in that: The mixture consists of polymer P A and an anode buffer layer material containing an anchoring group, wherein the anchoring group is selected from any of the following groups: The polymer P A Selected from photoactive layer polymer donor materials.

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