TW202415727A

TW202415727A - Composition

Info

Publication number: TW202415727A
Application number: TW112122932A
Authority: TW
Inventors: 格洛斯尼爾亞柯比; 蘇菲瓊斯; 戚蘭坎特卡
Original assignee: 日商住友化學股份有限公司
Priority date: 2022-10-11
Filing date: 2023-06-19
Publication date: 2024-04-16
Also published as: GB2623329A; GB202214997D0; WO2024079127A1

Abstract

A composition comprising an electron-donating polymer and an electron acceptor wherein the electron-donating polymer comprises a benzo[1,2-b:4,5-b']dithiophene repeat unit and wherein a film of the electron-accepting material has a peak absorption wavelength greater than 1000 nm. The composition may be used as a photosensitive layer of an organic photodetector.

Description

組合物Composition

本揭示案之實施例係關於適用於有機光偵測器的組合物。Embodiments of the present disclosure relate to compositions suitable for use in organic photodetectors.

已知包含有機半導體材料之一系列有機電子裝置，包括有機發光裝置、有機場效電晶體、有機光伏裝置及有機光偵測器(OPD)。A range of organic electronic devices comprising organic semiconductor materials are known, including organic light emitting devices, organic field effect transistors, organic photovoltaic devices and organic photodetectors (OPDs).

WO 2018/065352揭示一種具有光活性層的OPD，該光活性層含有：不含芙部分(fullerene moiety)的小分子受體以及具有供體及受體單元的共軛共聚物電子供體。WO 2018/065352 discloses an OPD having a photoactive layer, wherein the photoactive layer contains: a small molecule acceptor without a fullerene moiety and a co-polymer electron donor having donor and acceptor units.

WO 2018/065356揭示一種具有光活性層的OPD，該光活性層含有：不含芙部分的小分子受體以及無規分佈有供體及受體單元的共軛共聚物電子供體。WO 2018/065356 discloses an OPD having a photoactive layer, which contains: a small molecule acceptor without a phenotype and a co-polymer electron donor having randomly distributed donor and acceptor units.

Yao等人, "Design, Synthesis, and Photovoltaic Characterization of a Small Molecular Acceptor with an Ultra-Narrow Band Gap", Angew Chem Int Ed Engl. 2017年3月6日;56(11):3045-3049揭示具有1.24 eV帶隙之非芙受體。Yao et al., "Design, Synthesis, and Photovoltaic Characterization of a Small Molecular Acceptor with an Ultra-Narrow Band Gap", Angew Chem Int Ed Engl. 2017 Mar 6;56(11):3045-3049. Revealed a non-polyhedral acceptor with a 1.24 eV band gap.

Li等人, "Fused Tris(thienothiophene)‐Based Electron Acceptor with Strong Near‐Infrared Absorption for High‐Performance As‐Cast Solar Cells", Advanced Materials, 第30(10)卷, 2018揭示一種用於太陽能電池的稠合八環電子受體(FOIC)。Li et al., "Fused Tris(thienothiophene)‐Based Electron Acceptor with Strong Near‐Infrared Absorption for High‐Performance As‐Cast Solar Cells", Advanced Materials, Vol. 30(10), 2018, disclose a fused octacyclic electron acceptor (FOIC) for solar cells.

Gao等人, "A New Non-fullerene Acceptor with Near Infrared Absorption for High Performance Ternary‐Blend Organic Solar Cells with Efficiency over 13%" Advanced Science, 第5(6)卷, 2018年6月揭示一種太陽能電池，其含有受體-供體-受體(A-D-A)型非芙受體3TT-FIC，該受體具有三個稠合的噻吩并[3,2‐b]噻吩作為中央核心及經二氟取代之茚酮作為端基。Gao et al., "A New Non-fullerene Acceptor with Near Infrared Absorption for High Performance Ternary-Blend Organic Solar Cells with Efficiency over 13%" Advanced Science, Vol. 5(6), June 2018, disclose a solar cell containing an acceptor-donor-acceptor (A-D-A) type non-fullerene acceptor 3TT-FIC having three fused thieno[3,2-b]thiophenes as the central core and difluoro-substituted indanones as end groups.

Wang等人, "Fused Hexacyclic Nonfullerene Acceptor with Strong Near‐Infrared Absorption for Semitransparent Organic Solar Cells with 9.77% Efficiency"揭示含有受體IHIC的太陽能電池，該受體IHIC基於側接吸電子基1,1-二氰基亞甲基-3-茚酮的供電子基二噻吩環戊噻吩并[3,2- b]噻吩。 Wang et al., "Fused Hexacyclic Nonfullerene Acceptor with Strong Near-Infrared Absorption for Semitransparent Organic Solar Cells with 9.77% Efficiency" disclose solar cells containing an acceptor IHIC based on an electron-donating dithiophenecyclopentathieno[3,2- b ]thiophene flanked by an electron-withdrawing group 1,1-dicyanomethylene-3-indanone.

下文闡述本文所揭示之某些實施例之範疇的概要。應瞭解，此等範疇僅為了向讀者提供此等某些實施例的簡要概述而展現，並且不希望此等範疇限制本揭示案之範圍。實際上，本揭示案可涵蓋可未闡述的多種範疇及/或範疇組合。The following is a summary of the scope of certain embodiments disclosed herein. It should be understood that these scopes are presented only to provide the reader with a brief overview of these certain embodiments, and it is not intended that these scopes limit the scope of the present disclosure. In fact, the present disclosure may cover a variety of scopes and/or scope combinations that may not be described.

本揭示案之實施例提供包含供電子聚合物及受電子材料的組合物，其中該供電子聚合物包含苯并[1,2-b:4,5-b']二噻吩重複單元且其中受電子材料之膜具有大於1000 nm的峰值吸收波長。Embodiments of the present disclosure provide compositions comprising an electron donating polymer and an electron accepting material, wherein the electron donating polymer comprises benzo[1,2-b:4,5-b']dithiophene repeating units and wherein a film of the electron accepting material has a peak absorption wavelength greater than 1000 nm.

受電子材料較佳為非芙受體。The electron accepting material is preferably a non-porous acceptor.

在一較佳實施例中，電子受體為式(I)化合物： EAG - EDG - EAG (I) 其中各EAG為受電子基團；且EDG為式(II)或(III)之供電子基團： (II) (III) 各X獨立地為O或S； Ar ³及Ar ⁴在每次出現時獨立地為單環或多環芳族或雜芳族基團； Ar ⁵選自由以下組成之群：未取代或經一或兩個取代基取代的噻吩、呋喃及苯； R ¹及R ²在每次出現時獨立地為取代基； R ⁴及R ⁵各自獨立地為H或取代基； R ³及R ⁶各自獨立地為與EAG結合的H、取代基或二價基團； Z ¹為直接鍵或Z ¹與取代基R ⁴一起形成Ar ¹，其中Ar ¹為單環或多環芳族或雜芳族基團； Z ²為直接鍵或Z ²與取代基R ⁵一起形成Ar ²，其中Ar ²為單環或多環芳族或雜芳族基團； p為1、2或3； q為1、2或3；且 ---- 為連至EAG之連接點。 In a preferred embodiment, the electron acceptor is a compound of formula (I): EAG - EDG - EAG (I) wherein each EAG is an electron accepting group; and EDG is an electron donating group of formula (II) or (III): (II) (III) each X is independently O or S; Ar ³ and Ar ⁴ are independently monocyclic or polycyclic aromatic or heteroaromatic groups at each occurrence; Ar ⁵ is selected from the group consisting of thiophene, furan and benzene which are unsubstituted or substituted with one or two substituents; R ¹ and R ² are independently substituents at each occurrence; R ⁴ and R ⁵ are independently H or a substituent; R ³ and R ⁶ are independently H, a substituent or a divalent group bound to EAG; Z ¹ is a direct bond or Z ¹ and substituent R ⁴ together form Ar ¹ , wherein Ar ¹ is a monocyclic or polycyclic aromatic or heteroaromatic group; Z ² is a direct bond or Z ² and substituent R ⁵ together form Ar ² , wherein Ar ² is a monocyclic or polycyclic aromatic or heteroaromatic group; p is 1, 2, or 3; q is 1, 2, or 3; and ---- is the connection point to EAG.

在一些實施例中，提供一種調配物，其包含溶解或分散於一種或多種溶劑中的如本文所述之組合物。In some embodiments, a formulation is provided that includes a composition as described herein dissolved or dispersed in one or more solvents.

在一些實施例中，提供一種有機光偵測器，其包含：陽極；陰極；以及安置於陽極與陰極之間的光敏有機層，其中該光敏有機層包含如本文所述之組合物。In some embodiments, an organic photodetector is provided, comprising: an anode; a cathode; and a photosensitive organic layer disposed between the anode and the cathode, wherein the photosensitive organic layer comprises a composition as described herein.

在一些實施例中，提供一種電路，其包含如本文所述的有機光偵測器及以下中之至少一者：用於向有機光偵測器施加反向偏壓的電壓源及經組態以量測光偵測器所產生之光電流的裝置。In some embodiments, a circuit is provided that includes an organic photodetector as described herein and at least one of: a voltage source for applying a reverse bias to the organic photodetector and a device configured to measure a photocurrent generated by the photodetector.

在一些實施例中，提供一種形成如本文所述之有機光偵測器的方法，其包含在陽極及陰極中之一者上形成光敏有機層及在該光敏有機層上形成陽極及陰極中之另一者。In some embodiments, a method of forming an organic photodetector as described herein is provided, comprising forming a photosensitive organic layer on one of an anode and a cathode and forming the other of the anode and the cathode on the photosensitive organic layer.

本發明人進一步發現，含有包含苯并[1,2-b:4,5-b']二噻吩重複單元之供體聚合物的OPD可達成高外部量子效率與低暗電流之間的良好平衡，尤其在較長波長下。The inventors have further discovered that OPDs containing donor polymers comprising benzo[1,2-b:4,5-b']dithiophene repeating units can achieve a good balance between high external quantum efficiency and low dark current, especially at longer wavelengths.

因此，在一些實施例中，提供一種光感測器，其包含光源及如本文所述的有機光偵測器，該有機光偵測器經組態以偵測光源所發射的光。Thus, in some embodiments, a photo sensor is provided that includes a light source and an organic photodetector as described herein, the organic photodetector being configured to detect light emitted by the light source.

在一些實施例中，提供一種測定樣品中之目標材料之存在及/或濃度的方法，該方法包括：照射樣品以及量測如本文所述之有機光偵測器的反應，該有機光偵測器經組態以接收樣品在照射後所發射的光。In some embodiments, a method of determining the presence and/or concentration of a target material in a sample is provided, the method comprising: irradiating the sample and measuring the response of an organic photodetector as described herein, the organic photodetector being configured to receive light emitted by the sample after irradiation.

除非上下文另外明確要求，否則在通篇說明書及申請專利範圍中，字詞「包含(comprise)」、「包含(comprising)」及類似形式應以包括性意義解釋，而非以排他性或窮盡性意義解釋；亦即，以「包括但不限於」之意義來解釋。如本文所用，術語「連接(connected)」、「耦接(coupled)」或其任何變型意謂兩個或更多個元件之間的任何直接或間接連接或耦接；元件之間的耦接或連接可為物理的、邏輯的、電磁的或其組合。另外，當用於本申請案中時，字詞「本文中(herein)」、「上文(above)」、「下文(below)」及類似含義之字詞係指本申請案整體而非本申請案之任何特定部分。在上下文允許之情況下，實施方式中使用單數或複數之字詞亦可分別包括複數或單數。字詞「或」在提及兩項或更多項之清單時涵蓋該字詞之所有以下解譯：清單中之任一項、清單中之所有項及清單中之各項的任何組合。Unless the context clearly requires otherwise, throughout the specification and claims, the words "comprise," "comprising," and similar forms are to be interpreted in an inclusive sense and not in an exclusive or exhaustive sense; that is, in the sense of "including but not limited to." As used herein, the terms "connected," "coupled," or any variations thereof, mean any direct or indirect connection or coupling between two or more elements; the coupling or connection between elements may be physical, logical, electromagnetic, or a combination thereof. In addition, when used in this application, the words "herein," "above," "below," and words of similar meaning refer to this application as a whole and not to any particular portions of this application. Where the context permits, words used in the embodiments in the singular or plural may also include the plural or singular respectively. The word "or" when referring to a list of two or more items includes all of the following interpretations of the word: any one of the items in the list, all of the items in the list, and any combination of the items in the list.

本文所提供之技術的教示內容可以應用於其他系統，而不一定為下述系統。下述各種實例之元件及作用可加以組合以提供技術之其他實施方案。一些替代的技術實施方案不僅可包括下文提及之彼等實施方案的額外元件，而且可包括更少的元件。The teachings of the technology provided herein can be applied to other systems, not necessarily the following systems. The elements and functions of the various examples described below can be combined to provide other implementations of the technology. Some alternative technical implementations may include not only the additional elements of the implementations mentioned below, but also fewer elements.

可根據以下詳細描述對技術進行此等及其他變化。雖然說明書描述技術之某些實例，且描述所考慮之最佳模式，不論說明如何詳細地呈現，可以多種方式來實施該技術。系統細節的具體實施方案可顯著變化，同時仍被本文所揭示之技術涵蓋。如上文所提及，在描述技術之某些特徵或範疇時，所用特定術語不應理解為暗示該術語在本文中重新定義為受限於與彼術語相關之技術的任何具體特徵、特點或範疇。一般而言，除非實施方式章節明確定義此類術語，否則以下申請專利範圍中所使用之術語不應解釋為將該技術限於說明書中所揭示之具體實例。因此，技術之實際範疇不僅涵蓋所揭示之實例，而且涵蓋根據申請專利範圍來實施或執行該技術的所有等效方式。These and other variations may be made to the technology in light of the detailed description below. Although the specification describes certain examples of the technology and describes the best modes contemplated, no matter how detailed the description is presented, the technology can be implemented in a variety of ways. Specific implementations of system details may vary significantly while still being covered by the technology disclosed herein. As mentioned above, when describing certain features or scopes of the technology, the use of a particular term should not be understood to imply that the term is redefined herein as being limited to any specific feature, characteristic, or scope of the technology associated with that term. In general, unless such terms are expressly defined in the implementation section, the terms used in the following claims should not be interpreted as limiting the technology to the specific examples disclosed in the specification. Therefore, the actual scope of the technology covers not only the examples disclosed, but also all equivalent ways of implementing or performing the technology according to the scope of the claims.

為減少請求項之數目，下文以某些申請專利範圍形式呈現技術之某些範疇，但本申請人以任何數目個請求項形式考慮技術之各種態樣。舉例而言，雖然技術之一些範疇可敍述為電腦可讀媒體請求項，但其他範疇同樣可作為電腦可讀媒體請求項或以其他形式實施，諸如以手段加功能請求項實施。To reduce the number of claims, certain aspects of the technology are presented below in certain claim scope forms, but the applicants contemplate various aspects of the technology in any number of claim forms. For example, while some aspects of the technology may be described as computer-readable medium claims, other aspects may also be implemented as computer-readable medium claims or in other forms, such as means-plus-function claims.

在以下描述中，出於解釋之目的，闡述諸多具體細節以便透徹瞭解所揭示技術之實施方案。然而，熟習此項技術者將顯而易見，可在一些此等特定細節不存在的情況下實施所揭示技術之實施例。In the following description, for the purpose of explanation, many specific details are set forth in order to provide a thorough understanding of the embodiments of the disclosed technology. However, it will be apparent to those skilled in the art that the embodiments of the disclosed technology can be implemented without these specific details.

圖1繪示根據本揭示案之一些實施例的OPD。OPD包含陰極103、陽極107及安置於該陽極與該陰極之間的本體異質接面層105。OPD可支撐於基板101上，該基板視情況為玻璃或塑膠基板。FIG1 shows an OPD according to some embodiments of the present disclosure. The OPD includes a cathode 103, an anode 107, and a bulk heterojunction layer 105 disposed between the anode and the cathode. The OPD may be supported on a substrate 101, which may be a glass or plastic substrate.

圖1繪示其中陰極安置於基板與陽極之間的佈置。在其他實施例中，陽極可安置於陰極與基板之間。Figure 1 shows an arrangement in which the cathode is disposed between the substrate and the anode. In other embodiments, the anode may be disposed between the cathode and the substrate.

本體異質接面層包含電子受體與電子供體之混合物。在一些實施例中，本體異質接面層由電子受體及電子供體組成。在一些實施例中，本體異質接面層包含另一種電子受體。視情況，該另一種電子受體為芙。The bulk heterojunction layer comprises a mixture of an electron acceptor and an electron donor. In some embodiments, the bulk heterojunction layer is composed of an electron acceptor and an electron donor. In some embodiments, the bulk heterojunction layer comprises another electron acceptor. Optionally, the other electron acceptor is .

陽極及陰極中之每一者可獨立地為單個導電層，或可包含複數個層。Each of the anode and cathode may independently be a single conductive layer, or may include a plurality of layers.

OPD可包含除陽極、陰極及本體之外的層，如圖1中所示。在一些實施例中，電洞傳輸層安置於陽極與本體異質接面層之間。在一些實施例中，電子傳輸層安置於陰極與本體異質接面層之間。在一些實施例中，工作函數修改層安置於本體異質接面層與陽極之間及/或本體異質接面層與陰極之間。The OPD may include layers other than the anode, cathode, and bulk, as shown in FIG1. In some embodiments, a hole transport layer is disposed between the anode and the bulk heterojunction layer. In some embodiments, an electron transport layer is disposed between the cathode and the bulk heterojunction layer. In some embodiments, a work function modification layer is disposed between the bulk heterojunction layer and the anode and/or between the bulk heterojunction layer and the cathode.

在使用時，如本揭示案中所述的光偵測器可連接至用於向裝置施加反向偏壓的電壓源及/或經組態以量測光電流的裝置。向光偵測器施加之電壓可變化。在一些實施例中，光偵測器在使用時可連續偏壓。In use, a photodetector as described in the present disclosure may be connected to a voltage source for applying a reverse bias to the device and/or a device configured to measure photocurrent. The voltage applied to the photodetector may be varied. In some embodiments, the photodetector may be continuously biased in use.

在一些實施例中，光偵測器系統包含如本文所述之複數個光偵測器，諸如相機之影像感測器。In some embodiments, a photodetector system includes a plurality of photodetectors as described herein, such as an image sensor of a camera.

在一些實施例中，感測器可包含如本文所述之OPD及光源，其中該OPD經組態以接收自光源發射的光。In some embodiments, a sensor may include an OPD as described herein and a light source, wherein the OPD is configured to receive light emitted from the light source.

在一些實施例中，來自光源之光在到達OPD之前可或可不改變。舉例而言，光可在其到達OPD之前經過濾、降頻轉換或升頻轉換。In some embodiments, the light from the light source may or may not be altered before reaching the OPD. For example, the light may be filtered, down-converted, or up-converted before it reaches the OPD.

在一些實施例中，光源具有大於750 nm、視情況小於1500 nm之峰值波長。In some embodiments, the light source has a peak wavelength greater than 750 nm, optionally less than 1500 nm.

本體異質接面層可含有式(I)之電子受體(n型)化合物： EAG - EDG - EAG (I) 其中各EAG為受電子基團；且EDG為供電子基團。供電子基團可式(II)或(III)之基團： (II) (III) 其中：各X獨立地為O或S； Ar ³及Ar ⁴在每次出現時獨立地為單環或多環芳族或雜芳族基團； Ar ⁵選自由以下組成之群：未取代或經一或兩個取代基取代的噻吩、呋喃及苯； R ¹及R ²在每次出現時獨立地為取代基； R ⁴及R ⁵各自獨立地為H或取代基； R ³及R ⁶各自獨立地為與EAG結合的H、取代基或二價基團； Z ¹為直接鍵或Z ¹與取代基R ⁴一起形成Ar ¹，其中Ar ¹為單環或多環芳族或雜芳族基團； Z ²為直接鍵或Z ²與取代基R ⁵一起形成Ar ²，其中Ar ²為單環或多環芳族或雜芳族基團； p為1、2或3； q為1、2或3；且 ---- 為連至EAG之連接點。 The bulk heterojunction layer may contain an electron acceptor (n-type) compound of formula (I): EAG - EDG - EAG (I) wherein each EAG is an electron acceptor group; and EDG is an electron donating group. The electron donating group may be a group of formula (II) or (III): (II) (III) wherein: each X is independently O or S; Ar ³ and Ar ⁴ are independently monocyclic or polycyclic aromatic or heteroaromatic groups at each occurrence; Ar ⁵ is selected from the group consisting of thiophene, furan and benzene which are unsubstituted or substituted with one or two substituents; R ¹ and R ² are independently substituents at each occurrence; R ⁴ and R ⁵ are independently H or a substituent; R ³ and R ⁶ are independently H, a substituent or a divalent group bound to EAG; Z ¹ is a direct bond or Z ¹ and substituent R ⁴ together form Ar ¹ , wherein Ar ¹ is a monocyclic or polycyclic aromatic or heteroaromatic group; Z ² is a direct bond or Z ² and substituent R ⁵ together form Ar ² , wherein Ar ² is a monocyclic or polycyclic aromatic or heteroaromatic group; p is 1, 2, or 3; q is 1, 2, or 3; and ---- is the connection point to EAG.

本發明人已發現，式(I)化合物能夠吸收較長波長的光，例如大於750 nm、視情況大於1000 nm、視情況小於1500 nm，從而允許將此等化合物用於有機光偵測器，尤其用於含有此類OPD及近紅外光源的光感測器。The inventors have found that the compounds of formula (I) are capable of absorbing light of longer wavelengths, for example greater than 750 nm, preferably greater than 1000 nm, preferably less than 1500 nm, thereby allowing these compounds to be used in organic photodetectors, especially in light sensors containing such OPDs and near-infrared light sources.

視情況，式(Ia)或(Ib)之R ¹及R ²在每次出現時獨立地選自由以下組成之群：直鏈、分支鏈或環狀C _1-20烷基，其中一個或多個不相鄰的非末端C原子可經O、S、NR ¹²、CO或COO置換，其中R ¹²為C _1-12烴基且該C _1-20烷基中的一個或多個H原子可經F置換；且式(Ak)u-(Ar ⁶)v之基團，其中Ak為C _1-12伸烷基鏈，其中一個或多個C原子可經O、S、CO或COO置換；u為0或1；Ar ⁶在每次出現時獨立地為未取代或經一個或多個取代基取代的芳族或雜芳族基團；且v至少為1，視情況為1、2或3。 As the case may be, R ¹ and R ² of formula (Ia) or (Ib) are independently selected at each occurrence from the group consisting of: a linear, branched or cyclic C _1-20 alkyl group, wherein one or more non-adjacent non-terminal C atoms may be replaced by O, S, NR ¹² , CO or COO, wherein R ¹² is a C _1-12 alkyl group and one or more H atoms in the C _1-20 alkyl group may be replaced by F; and a group of formula (Ak)u-(Ar ⁶ )v, wherein Ak is a C _1-12 alkylene chain, wherein one or more C atoms may be replaced by O, S, CO or COO; u is 0 or 1; Ar ⁶ is independently at each occurrence an aromatic or heteroaromatic group which is unsubstituted or substituted with one or more substituents; and v is at least 1, and is 1, 2 or 3 as appropriate.

C _1-12烴基可為C _1-12烷基；未取代之苯基；以及經一個或多個C _1-6烷基取代之苯基。 The C _1-12 alkyl group may be a C _1-12 alkyl group; an unsubstituted phenyl group; and a phenyl group substituted by one or more C _1-6 alkyl groups.

Ar ⁶較佳為苯基。 Ar ⁶ is preferably phenyl.

當存在時，Ar ⁶之取代基可為取代基R ¹⁶，其中R ¹⁶在每次出現時獨立地選自C _1-20烷基，其中一個或多個不相鄰的非末端C原子可經O、S、NR ¹²、CO或COO置換且C _1-20烷基中的一個或多個H原子可經F置換。 When present, a substituent of ^Ar6 may be a substituent ^R16 , wherein ^R16 at each occurrence is independently selected from _C1-20 alkyl, wherein one or more non-adjacent non-terminal C atoms may be replaced by O, S, ^NR12 , CO or COO and one or more H atoms in the _C1-20 alkyl may be replaced by F.

若v為3或更大，則-(Ar ⁶)v可為Ar ⁶基團之直鏈或分支鏈。如本文所述的Ar基團之直鏈僅具有一個單價末端Ar ⁶基團，而Ar ⁶基團之分支鏈具有至少兩個單價末端Ar ⁶基團。 If v is 3 or more, -(Ar ⁶ )v can be a straight chain or a branched chain of an Ar ⁶ group. A straight chain of an Ar group as described herein has only one monovalent terminal Ar ⁶ group, while a branched chain of an Ar ⁶ group has at least two monovalent terminal Ar ⁶ groups.

視情況，R ¹及R ²中之至少一者在每次出現時為苯基，該苯基未取代或經一或多個選自如上文所述之R ¹⁶的取代基取代。 Optionally, at least one of R ¹ and R ² at each occurrence is phenyl, which is unsubstituted or substituted with one or more substituents selected from R ¹⁶ as described above.

視情況，各R ³至R ⁶獨立地選自： H； C _1-12烷基，其中一個或多個不相鄰的非末端C原子可經O、S、COO或CO置換；且芳族或雜芳族基團Ar ⁶，其未取代或經一個或多個取代基取代。 Optionally, each R ³ to R ⁶ is independently selected from: H; C _1-12 alkyl, wherein one or more non-adjacent non-terminal C atoms may be replaced by O, S, COO or CO; and an aromatic or heteroaromatic group Ar ⁶ which is unsubstituted or substituted by one or more substituents.

Ar ⁶較佳為芳族基團，更佳為苯基。 Ar ⁶ is preferably an aromatic group, more preferably a phenyl group.

存在時，Ar ⁶之一個或多個取代基可選自C _1-12烷基，其中一個或多個不相鄰的非末端C原子可經O、S、COO或CO置換。 When present, one or more substituents of ^Ar6 may be selected from _C1-12 alkyl, wherein one or more non-adjacent non-terminal C atoms may be replaced by O, S, COO or CO.

如本文所用，烷基之「非末端」C原子意謂除直鏈(正烷基)之甲基C原子或分支鏈烷基鏈之甲基C原子以外的烷基C原子。As used herein, a "non-terminal" C atom of an alkyl group means an alkyl C atom other than a methyl C atom of a straight chain (n-alkyl) or a methyl C atom of a branched alkyl chain.

視情況，Ar ³及Ar ⁴各自獨立地選自噻吩、呋喃、雙呋喃及噻吩并噻吩。 Optionally, Ar ³ and Ar ⁴ are each independently selected from thiophene, furan, difuran and thienothiophene.

Ar ³、Ar ⁴及Ar ⁵各自獨立地未取代或經一個或多個取代基取代。存在時，Ar ³、Ar ⁴及Ar ⁵之較佳取代基係選自除H之外的上述基團R ³至R ⁶，較佳為C _1-20烷基，其中一個或多個不相鄰的非末端C原子經O、S、CO或COO置換。 Ar ³ , Ar ⁴ and Ar ⁵ are each independently unsubstituted or substituted with one or more substituents. When present, preferred substituents for Ar ³ , Ar ⁴ and Ar ⁵ are selected from the above groups R ³ to R ⁶ except H, preferably C _1-20 alkyl, wherein one or more non-adjacent non-terminal C atoms are replaced by O, S, CO or COO.

視情況，EDG選自式(IIa)及(IIIa)： (IIa) (IIIa) As appropriate, EDG is selected from formula (IIa) and (IIIa): (IIa) (IIIa)

視情況，EDG選自式(IIb)及(IIIb)： (IIb) (IIIb) 其中R ⁷在每次出現時獨立地為H或取代基。 As appropriate, EDG is selected from formula (IIb) and (IIIb): (IIb) (IIIb) wherein R ⁷ at each occurrence is independently H or a substituent.

視情況，R ⁷在每次出現時獨立地選自： H； C _1-12烷基，其中一個或多個不相鄰的非末端C原子可經O、S、COO或CO置換；且芳族或雜芳族基團Ar ⁶，其未取代或經一個或多個取代基取代。 Optionally, R ⁷ is independently selected at each occurrence from: H; C _1-12 alkyl, wherein one or more non-adjacent non-terminal C atoms may be replaced by O, S, COO or CO; and an aromatic or heteroaromatic group Ar ⁶ , which is unsubstituted or substituted by one or more substituents.

在一些實施例中，各R ³至R ⁶及存在時的R ⁷為H；C _1-20烷基；或C _1-20烷氧基。 In some embodiments, each of R ³ to R ⁶ and R ⁷ when present is H; C _1-20 alkyl; or C _1-20 alkoxy.

在一些實施例中，R ⁴與R ⁵中之至少一者、視情況兩者均不為H，且各R ³、R ⁶及存在時的R ⁷為H。 In some embodiments, at least one, optionally both, of ^R4 and ^R5 are not H, and each of ^R3 , ^R6 , and when present, ^R7 is H.

視情況，p及q中之至少一者為2。As the case may be, at least one of p and q is 2.

視情況，Z ¹連接至R ⁴以形成單環芳族或雜芳族基團且/或Z ²連接至R ⁵以形成單環芳族或雜芳族基團。 Optionally, ^Z1 is linked to ^R4 to form a monocyclic aromatic or heteroaromatic group and/or ^Z2 is linked to ^R5 to form a monocyclic aromatic or heteroaromatic group.

視情況，Z ¹連接至R ⁴以形成噻吩環或呋喃環且/或Z ²連接至R ⁵以形成噻吩環或呋喃環。 Optionally, ^Z1 is linked to ^R4 to form a thiophene ring or a furan ring and/or ^Z2 is linked to ^R5 to form a thiophene ring or a furan ring.

各EAG的LUMO能級比EDG更深(亦即，距離真空能級更遠)，較佳深至少1 eV。EAG及EDG之LUMO能級可藉由將EAG-H之LUMO能級與H-EDG-H之LUMO能級模型化來測定，亦即，藉由用氫原子鍵置換EAG與EDG之間的鍵來測定。可使用獲自Gaussian的Gaussian09軟體、使用具有B3LYP (泛函)及LACVP* (基底函數組)的Gaussian09進行模型化。The LUMO level of each EAG is deeper (i.e., farther from the vacuum level) than that of EDG, preferably at least 1 eV deeper. The LUMO levels of EAG and EDG can be determined by modeling the LUMO level of EAG-H with the LUMO level of H-EDG-H, i.e., by replacing the bond between EAG and EDG with a hydrogen atom bond. Modeling can be performed using Gaussian09 software obtained from Gaussian, using Gaussian09 with B3LYP (functional) and LACVP* (basis function set).

視情況，各EAG為式(IV)或(V)之基團： (IV) (V) 其中A為未取代或經一個或多個取代基取代的5員或6員環；R ¹⁰及R ¹¹在每次出現時獨立地為取代基；且Ar ⁷為未取代或經一個或多個取代基取代的芳族或雜芳族基團。 Each EAG is a group of formula (IV) or (V), as appropriate: (IV) (V) wherein A is a 5- or 6-membered ring which is unsubstituted or substituted with one or more substituents; R ¹⁰ and R ¹¹ are independently a substituent at each occurrence; and Ar ⁷ is an aromatic or heteroaromatic group which is unsubstituted or substituted with one or more substituents.

視情況，各EAG為式(VI)之基團： (VI) 其中： R ¹⁰在每次出現時為H或取代基； ---- 表示連至EDG的連接位置；且各X ¹至X ⁴獨立地為CR ¹³或N，其中R ¹³在每次出現時為H或取代基。 Optionally, each EAG is a group of formula (VI): (VI) wherein: R ¹⁰ is H or a substituent at each occurrence; ---- represents the attachment position to EDG; and each X ¹ to X ⁴ is independently CR ¹³ or N, wherein R ¹³ is H or a substituent at each occurrence.

視情況，各R ¹³獨立地選自H；C _1-12烷基；及吸電子基團。視情況，吸電子基團為F或CN。 Optionally, each R ¹³ is independently selected from H; C _1-12 alkyl; and an electron-withdrawing group. Optionally, the electron-withdrawing group is F or CN.

R ¹⁰較佳為H。 R ¹⁰ is preferably H.

取代基R ¹⁰較佳選自由以下組成之群：C _1-12烷基，其中一個或多個不相鄰的非末端C原子可經O、S、COO或CO置換且該烷基中的一個或多個H原子可經F置換；及芳族基團Ar ⁹，視情況為苯基，其未取代或經一個或多個選自F及C _1-12烷基的取代基取代，其中一個或多個不相鄰的非末端C原子可經O、S、COO或CO置換。 The substituent R ¹⁰ is preferably selected from the group consisting of: C _1-12 alkyl, wherein one or more non-adjacent non-terminal C atoms may be replaced by O, S, COO or CO and one or more H atoms in the alkyl may be replaced by F; and an aromatic group Ar ⁹ , optionally phenyl, which is unsubstituted or substituted by one or more substituents selected from F and C _1-12 alkyl, wherein one or more non-adjacent non-terminal C atoms may be replaced by O, S, COO or CO.

視情況，R ³及/或R ⁶為B(R ¹⁴) ₂，其中R ¹⁴在每次出現時為取代基，視情況為C _1-20烴基，且一個或兩個EAG基團未取代或經式(VII)之雜芳族基團取代： (VII) 其中Ar ⁸為單環或稠合的雜芳族基團，其未取代或經一個或多個取代基取代；→為連至R ³或R ⁶之硼原子的鍵；且---為連至EDG的鍵。 Optionally, R ³ and/or R ⁶ is B(R ¹⁴ ) ₂ , wherein R ¹⁴ is a substituent at each occurrence, optionally a C _1-20 alkyl group, and one or both EAG groups are unsubstituted or substituted with a heteroaromatic group of formula (VII): (VII) wherein Ar ⁸ is a monocyclic or fused heteroaromatic group which is unsubstituted or substituted with one or more substituents; → is a bond to the boron atom of R ³ or R ⁶ ; and --- is a bond to EDG.

Ar ⁸(存在時)之取代基或各取代基可選自關於R ⁷所述的取代基。 The or each substituent for Ar ⁸ (when present) may be selected from the substituents described for R ⁷ .

視情況，R ¹⁴為C _1-20烴基，R ¹⁴選自C _1-12烷基；未取代之苯基；及經一個或多個C _1-12烷基取代之苯基。 Optionally, R ¹⁴ is a C _1-20 alkyl group, R ¹⁴ is selected from C _1-12 alkyl; unsubstituted phenyl; and phenyl substituted by one or more C _1-12 alkyl groups.

視情況，式(VII)之基團選自式(VIIa)、(VIIb)及(VIIc)：其中R ¹⁵在每次出現時獨立地為H或取代基，視情況為H或關於R ⁷所述的取代基。EDG、EAG及EDG之B(R ¹⁴) ₂取代基可連接在一起以形成5員或6員環。 Optionally, the group of formula (VII) is selected from formula (VIIa), (VIIb) and (VIIc): wherein R ¹⁵ is independently at each occurrence H or a substituent, optionally H or a substituent as described for R ^7. EDG, EAG and the B(R ¹⁴ ) ₂ substituents of EDG may be linked together to form a 5- or 6-membered ring.

視情況，EAG選自式(XIV)至(XXV)： (IXVa) (IXVb) (XVa) (XVb) (XVIa) (XVIb) (XVIc) (XVII) (XVIII) (XIX) (XX) (XXI) (XXII) (XXIV) (XXV) As appropriate, EAG is selected from formula (XIV) to (XXV): (IXVa) (IXVb) (XVa) (XVb) (XVIa) (XVIb) (XVIc) (XVII) (XVIII) (XIX) (XX) (XXI) (XXII) (XXIV) (XXV)

J為O或S。J is O or S.

A為5員或6員環，其未取代或經一個或多個取代基取代且可與一個或多個其他環稠合。A is a 5- or 6-membered ring, which is unsubstituted or substituted with one or more substituents and may be fused to one or more other rings.

R ²³在每次出現時為取代基，視情況為C _1-12烷基，其中一個或多個不相鄰的非末端C原子可經O、S、COO或CO置換，且烷基之一個或多個H原子可經F置換。 R ²³ is a substituent at each occurrence, optionally a C _1-12 alkyl group, wherein one or more non-adjacent non-terminal C atoms may be replaced by O, S, COO or CO, and one or more H atoms of the alkyl group may be replaced by F.

R ²⁵在每次出現時獨立地為H；F；C _1-12烷基，其中一個或多個不相鄰的非末端C原子可經O、S、COO或CO置換且該烷基中的一個或多個H原子可經F置換；或芳族基團Ar ²，視情況為苯基，其未取代或經一個或多個選自F及C _1-12烷基的取代基取代，其中一個或多個不相鄰的非末端C原子可經O、S、COO或CO置換。 R ²⁵ is independently at each occurrence H; F; C _1-12 alkyl, wherein one or more non-adjacent non-terminal C atoms may be replaced by O, S, COO or CO and one or more H atoms in the alkyl may be replaced by F; or an aromatic group Ar ² , optionally phenyl, which is unsubstituted or substituted by one or more substituents selected from F and C _1-12 alkyl, wherein one or more non-adjacent non-terminal C atoms may be replaced by O, S, COO or CO.

R ²⁶為取代基，較佳為選自以下的取代基： -(Ar ¹³) _w，其中Ar ¹³在每次出現時獨立地為未取代或經取代之芳基或雜芳基，較佳為噻吩，且w為1、2或3；；；；及 C _1-12烷基，其中一個或多個不相鄰的非末端C原子可經O、S、COO或CO置換且該烷基中的一個或多個H原子可經F置換。 R ²⁶ is a substituent, preferably a substituent selected from the following: -(Ar ¹³ ) _w , wherein Ar ¹³ is independently unsubstituted or substituted aryl or heteroaryl at each occurrence, preferably thiophene, and w is 1, 2 or 3; ; ; and C _1-12 alkyl, wherein one or more non-adjacent non-terminal C atoms may be replaced by O, S, COO or CO and one or more H atoms in the alkyl may be replaced by F.

Ar ¹⁴為5員雜芳族基團，較佳為噻吩或呋喃，其未取代或經一個或多個取代基取代。 Ar ¹⁴ is a 5-membered heteroaromatic group, preferably thiophene or furan, which is unsubstituted or substituted with one or more substituents.

當存在時，Ar ¹³及Ar ¹⁴之取代基視情況選自C _1-12烷基，其中一個或多個不相鄰的非末端C原子可經O、S、COO或CO置換且該烷基中的一個或多個H原子可經F置換。 When present, substituents for Ar ¹³ and Ar ¹⁴ are optionally selected from C _1-12 alkyl groups, wherein one or more non-adjacent non-terminal C atoms may be replaced by O, S, COO or CO and one or more H atoms in the alkyl group may be replaced by F.

Z ¹為N或P Z ¹ is N or P

T ¹、T ²及T ³各自獨立地表示可與一個或多個其他環稠合的芳基或雜芳基環。當存在時，T ¹、T ²及T ³之取代基視情況選自R ¹⁵之非H基團。 T ¹ , T ² and T ³ each independently represent an aryl or heteroaryl ring which may be fused to one or more other rings. When present, substituents for T ¹ , T ² and T ³ are optionally selected from non-H groups of R ¹⁵ .

式(XIVa)或(XIVb)之例示性化合物包括： ` 其中Ak為C _1-12伸烷基鏈，其中一個或多個C原子可經O、S、CO或COO置換；An為陰離子，視情況為-SO ₃ ^-；且各苯環獨立地為未取代或經一個或多個選自關於R ¹⁰所述之取代基的取代基取代。 Exemplary compounds of formula (XIVa) or (XIVb) include: ` wherein Ak is a C _1-12 alkylene chain, one or more C atoms of which may be replaced by O, S, CO or COO; An is an anion, optionally -SO ₃ ^- ; and each benzene ring is independently unsubstituted or substituted by one or more substituents selected from the substituents described for R ¹⁰ .

式(XXI)之例示性EAG為： Exemplary EAGs of formula (XXI) are:

式(XXII)之例示性EAG基團為： Exemplary EAG groups of formula (XXII) are:

例示性式(I)化合物為： Exemplary compounds of formula (I) are:

其中EH為乙基己基。Wherein EH is ethylhexyl.

本發明人已發現，ADA'DA型電子受體當與包含苯并[1,2-b:4,5-b']二噻吩重複單元的供電子聚合物組合使用時可提供高效率及/或低暗電流。ADA'DA型電子受體可為式(IX)化合物： (IX) 其中： D ¹及D ²在每次出現時獨立地為供電子基團； A ¹為二價受電子基團； A ²及A ³各自獨立地為單價受電子基團； B ¹及B ²在每次出現時獨立地為橋基； x1及x2各自獨立地為0、1、2或3； y1及y2各自獨立地為至少1；且 z1及z2彼此獨立地為0、1、2或3。 The inventors have found that ADA'DA type electron acceptors can provide high efficiency and/or low dark current when used in combination with electron donating polymers comprising benzo[1,2-b:4,5-b']dithiophene repeating units. The ADA'DA type electron acceptor can be a compound of formula (IX): (IX) wherein: ^D1 and ^D2 are independently electron donating groups at each occurrence; ^A1 is a divalent electron accepting group; ^A2 and ^A3 are independently monovalent electron accepting groups; ^B1 and ^B2 are independently bridging groups at each occurrence; x1 and x2 are independently 0, 1, 2 or 3; y1 and y2 are independently at least 1; and z1 and z2 are independently 0, 1, 2 or 3.

A ¹可選自本文中描述為受電子重複單元的基團，例如式(XVIIIa)至(XLI)之基團。 ^A1 can be selected from the groups described herein as electron accepting repeating units, such as groups of formula (XVIIIa) to (XLI).

A ²及A ³可選自如本文所述的受電子基團EAG，較佳為式(V)或(VI)之基團。A ²與A ³可相同或不同，較佳為相同的。 ^A2 and ^A3 can be selected from the electron accepting groups EAG as described herein, preferably the groups of formula (V) or (VI). ^A2 and ^A3 can be the same or different, preferably the same.

D ¹及D ²較佳為含有3個或更多個環的稠合雜芳族基團。尤其較佳的供電子基團D ¹及D ²包含稠合的噻吩或呋喃環，視情況為含有噻吩或呋喃環及選自以下之一個或多個環的稠合環：苯、環戊二烯、四氫哌喃、四氫硫哌喃及哌啶環，該等環中之每一者未取代或經一個或多個取代基取代。取代基可選自如本文所述的非H基團R ²⁵。 D ¹ and D ² are preferably fused heteroaromatic groups containing 3 or more rings. Particularly preferred electron-donating groups D ¹ and D ² include fused thiophene or furan rings, optionally fused rings containing a thiophene or furan ring and one or more rings selected from the following: benzene, cyclopentadiene, tetrahydropyran, tetrahydrothiopyran and piperidine ring, each of which is unsubstituted or substituted with one or more substituents. Substituents may be selected from non-H groups R ²⁵ as described herein.

例示性基團D ¹及D ²包括但不限於： Exemplary groups ^D1 and ^D2 include, but are not limited to:

其中R ²⁵如上文所述。 wherein R ²⁵ is as described above.

橋接單元B ¹及B ²較佳為單環或稠合的雙環伸芳基或伸雜芳基，更佳為單環或稠合的雙環伸雜芳基，最佳為噻吩或噻吩并噻吩。B ¹及B ²可未取代或經一個或多個取代基取代，視情況經一個或多個非H基團R ²⁵取代。 The bridging units ^B1 and ^B2 are preferably monocyclic or fused bicyclic aryl or heteroaryl, more preferably monocyclic or fused bicyclic heteroaryl, most preferably thiophene or thienothiophene. ^B1 and ^B2 may be unsubstituted or substituted with one or more substituents, optionally substituted with one or more non-H groups ^R25 .

非芙受體可與芙受體組合使用。Non-receptors can be used in combination with receptors.

非芙受體:芙受體重量比可在約1:0.1-1:1範圍內，較佳在約1:0.1-1:0.5內。The weight ratio of non-receptor:receptor may be in the range of about 1:0.1-1:1, preferably about 1:0.1-1:0.5.

芙可為C ₆₀、C ₇₀、C ₇₆、C ₇₈或C ₈₄芙或其衍生物，包括但不限於PCBM型芙衍生物(包括苯基-C61-丁酸甲酯(C ₆₀PCBM)及苯基-C71-丁酸甲酯(C ₇₀PCBM))、TCBM型芙衍生物(例如甲苯基-C61-丁酸甲酯(C ₆₀TCBM))及ThCBM型芙衍生物(例如噻吩基-C61-丁酸甲酯(C ₆₀ThCBM) The isocyanate may be _C60 , _C70 , _C76 , _C78 or _C84 isocyanate or a derivative thereof, including but not limited to PCBM-type isocyanate derivatives (including phenyl-C61-butyric acid methyl ester ( _C60 PCBM) and phenyl-C71-butyric acid methyl ester ( _C70 PCBM)), TCBM-type isocyanate derivatives (e.g. tolyl-C61-butyric acid methyl ester ( _C60 TCBM)) and ThCBM-type isocyanate derivatives (e.g. thienyl-C61-butyric acid methyl ester ( _C60 ThCBM)).

當存在時，芙受體可具有式(VIII)：其中A與芙之C-C基團一起形成可未取代或經一個或多個取代基取代之單環或稠環基團。 When present, the receptor may have the formula (VIII): wherein A and the CC group of R together form a monocyclic or condensed ring group which may be unsubstituted or substituted by one or more substituents.

例示性芙衍生物包括式(IIIa)、(IIIb)及(IIIc)：其中R ³⁰至R ⁴²各自獨立地為H或取代基。 Exemplary fluorine derivatives include formula (IIIa), (IIIb) and (IIIc): wherein R ³⁰ to R ⁴² are each independently H or a substituent.

取代基R ³⁰至R ⁴²在每次出現時視情況且獨立地選自由以下組成之群：芳基或雜芳基，視情況為苯基，其可未取代或經一個或多個取代基取代；以及C _1-20烷基，其中一個或多個不相鄰的非末端C原子可經O、S、CO或COO置換且一個或多個H原子可經F置換。 The substituents R ³⁰ to R ⁴² are optionally and independently selected at each occurrence from the group consisting of: aryl or heteroaryl, optionally phenyl, which may be unsubstituted or substituted with one or more substituents; and C _1-20 alkyl, wherein one or more non-adjacent non-terminal C atoms may be replaced by O, S, CO or COO and one or more H atoms may be replaced by F.

當存在時，芳基或雜芳基R ³⁰至R ⁴²之取代基視情況選自C _1-12烷基，其中一個或多個不相鄰的非末端C原子可經O、S、CO或COO置換且一個或多個H原子可經F置換。 When present, substituents of the aryl or heteroaryl R ³⁰ to R ⁴² are optionally selected from C _1-12 alkyl, wherein one or more non-adjacent non-terminal C atoms may be replaced by O, S, CO or COO and one or more H atoms may be replaced by F.

供體(p型)化合物不受特別限制且可適當地選自熟習此項技術者已知的供電子材料，包括有機聚合物及非聚合有機分子。p型化合物的HOMO比電子受體之LUMO更深(距離真空能級更遠)。視情況，p型供體之HOMO能級與n型受體化合物之LUMO能級之間的間隙小於1.4 eV。The donor (p-type) compound is not particularly limited and can be appropriately selected from electron donating materials known to those skilled in the art, including organic polymers and non-polymeric organic molecules. The HOMO of the p-type compound is deeper (farther from the vacuum energy level) than the LUMO of the electron acceptor. Optionally, the gap between the HOMO energy level of the p-type donor and the LUMO energy level of the n-type acceptor compound is less than 1.4 eV.

在一較佳實施例中，p型供體化合物為有機共軛聚合物，其可為包括交替、無規或嵌段共聚物之均聚物或共聚物。較佳的交替共聚物包含供電子重複單元及受電子重複單元。較佳為非結晶或半結晶共軛有機聚合物。更佳地，p型有機半導體為具有低帶隙的共軛有機聚合物，該帶隙典型地在2.5 eV與1.5 eV之間，較佳在2.3 eV與1.8 eV之間。作為例示性p型供體聚合物，可提及選自共軛烴或雜環聚合物之聚合物，包括聚并苯、聚苯胺、聚薁、聚苯并呋喃、聚茀、聚呋喃、聚茚并茀、聚吲哚、聚苯、聚吡唑啉、聚芘、聚嗒、聚吡啶、聚三芳基胺、聚(伸苯基乙烯)、聚(3-取代之噻吩)、聚(3,4-雙取代之噻吩)、聚硒吩、聚(3-取代之硒吩)、聚(3,4-雙取代之硒吩)、聚(雙噻吩)、聚(三噻吩)、聚(雙硒吩)、聚(三硒吩)、聚噻吩并[2,3-b]噻吩、聚噻吩并[3,2-b]噻吩、聚苯并噻吩、聚苯并[1,2-b:4,5-b']二噻吩、聚異苯并噻吩、聚(單取代之吡咯)、聚(3,4-雙取代之吡咯)、聚-1,3,4- 二唑、聚異硫茚、其衍生物及共聚物。p型供體之較佳實例為聚茀與聚噻吩(其中之每一者可經取代)之共聚物，及包含基於苯并噻二唑及基於噻吩之重複單元(其中之每一者可經取代)的聚合物。應理解，p型供體亦可由複數種供電子材料之混合物組成。 In a preferred embodiment, the p-type donor compound is an organic conjugated polymer, which may be a homopolymer or copolymer including alternating, random or block copolymers. Preferred alternating copolymers contain electron donating repeating units and electron accepting repeating units. Preferably, it is a non-crystalline or semi-crystalline conjugated organic polymer. More preferably, the p-type organic semiconductor is a conjugated organic polymer with a low band gap, which is typically between 2.5 eV and 1.5 eV, preferably between 2.3 eV and 1.8 eV. As exemplary p-type donor polymers, there can be mentioned polymers selected from conjugated hydrocarbons or heterocyclic polymers, including polyphenylenes, polyanilines, polyazulenes, polybenzofurans, polyfluorenes, polyfurans, polyindenofluorenes, polyindoles, polyphenylenes, polypyrazolines, polypyrenes, polytantalums, polypyrrolidine ... , polypyridine, polytriarylamine, poly(phenylene vinylene), poly(3-substituted thiophene), poly(3,4-bissubstituted thiophene), polyselenophene, poly(3-substituted selenophene), poly(3,4-bissubstituted selenophene), poly(bisthiophene), poly(terthiophene), poly(bisselenophene), poly(triselenophene), polythieno[2,3-b]thiophene, polythieno[3,2-b]thiophene, polybenzothiophene, polybenzo[1,2-b:4,5-b']dithiophene, polyisobenzothiophene, poly(monosubstituted pyrrole), poly(3,4-bissubstituted pyrrole), poly-1,3,4- oxadiazole, polyisothiophene, its derivatives and copolymers. Preferred examples of p-type donors are copolymers of polyfluorene and polythiophene (each of which may be substituted), and polymers comprising benzothiadiazole-based and thiophene-based repeating units (each of which may be substituted). It should be understood that the p-type donor may also be composed of a mixture of a plurality of electron-donating materials.

視情況，供體聚合物包含式(XXX)之重複單元： (XXX) 其中R ⁵⁰及R ⁵¹在每次出現時獨立地為H或取代基。 Optionally, the donor polymer comprises repeating units of formula (XXX): (XXX) wherein R ⁵⁰ and R ⁵¹ at each occurrence are independently H or a substituent.

取代基R ⁵⁰及R ⁵¹可選自關於R ⁷所述之除H之外的基團。 The substituents R ⁵⁰ and R ⁵¹ may be selected from the groups described with respect to R ⁷ except H.

較佳地，各R ⁵⁰為取代基。在一較佳實施例中，連接R ⁵⁰基團以形成-Y ¹-C(R ⁵²) ₂-之基團，其中Y ¹為O、NR ⁵³或C(R ⁵²) ₂；R ⁵²在每次出現時為H或取代基，較佳為如關於R ¹所述的取代基，最佳為C _1-30烴基；且R ⁵³為取代基，較佳為C _1-30烴基。 Preferably, each R ⁵⁰ is a substituent. In a preferred embodiment, the R ⁵⁰ groups are linked to form a group of -Y ¹ -C(R ⁵² ) ₂ -, wherein Y ¹ is O, NR ⁵³ or C(R ⁵² ) ₂ ; R ⁵² is H or a substituent at each occurrence, preferably a substituent as described for R ¹ , most preferably a C _1-30 alkyl group; and R ⁵³ is a substituent, preferably a C _1-30 alkyl group.

較佳地，各R ⁵¹為H。 Preferably, each R ⁵¹ is H.

視情況，聚合物包含式(X)之供電子苯并[1,2-b:4,5-b']二噻吩重複單元： (X) 其中R ¹⁷及R ¹⁸各自獨立地選自H；F；C _1-20烷基，其中一個或多個不相鄰的非末端C原子可經O、S、COO或CO置換且該烷基中的一個或多個H原子可經F置換；或芳族基團或雜芳族基團Ar ¹⁰，其未取代或經一個或多個選自以下的取代基取代：F及C _1-12烷基，其中一個或多個不相鄰的非末端C原子可經O、S、COO或CO置換。 Optionally, the polymer comprises electron donating benzo[1,2-b:4,5-b']dithiophene repeating units of formula (X): (X) wherein R ¹⁷ and R ¹⁸ are each independently selected from H; F; a C _1-20 alkyl group, wherein one or more non-adjacent non-terminal C atoms may be replaced by O, S, COO or CO and one or more H atoms in the alkyl group may be replaced by F; or an aromatic group or a heteroaromatic group Ar ¹⁰ which is unsubstituted or substituted by one or more substituents selected from F and a C _1-12 alkyl group, wherein one or more non-adjacent non-terminal C atoms may be replaced by O, S, COO or CO.

Ar ¹⁰較佳未取代或經噻吩取代。 Ar ¹⁰ is preferably unsubstituted or substituted with thiophene.

各R ¹⁷較佳選自未取代或經取代的噻吩及C _1-11烷氧基。 Each R ¹⁷ is preferably selected from unsubstituted or substituted thiophene and C _1-11 alkoxy.

視情況，供體聚合物包含選自下式之重複單元的受電子重複單元： (XVIIIa) (XIXa) (XXa) (XXIa) (XXIIa) (XXIVa) (XXVa) (XXXVIa) (XXXVIIa) (XXXVIIIa) XL XLI 其中R ²⁵、Z ¹、R ²³及R ²⁵如上文所述且其中R ²⁷及R ²⁸各自獨立地選自H或取代基，更佳選自吸電子取代基。例示性吸電子取代基為F；CN；NO ₂；及COOR ²⁹，其中R ²⁹為C _1-20烴基，視情況為C _1-12烷基或苯基，其視情況經一個或多個C _1-12烷基取代。 Optionally, the donor polymer comprises electron accepting repeating units selected from repeating units of the formula: (XVIIIa) (XIXa) (XXa) (XXIa) (XXIIa) (XXIVa) (XXVa) (XXXVIa) (XXXVIIa) (XXXVIIIa) XL XLI wherein R ²⁵ , Z ¹ , R ²³ and R ²⁵ are as described above and wherein R ²⁷ and R ²⁸ are each independently selected from H or a substituent, more preferably an electron withdrawing substituent. Exemplary electron withdrawing substituents are F; CN; NO ₂ ; and COOR ²⁹ , wherein R ²⁹ is C _1-20 alkyl, optionally C _1-12 alkyl or phenyl, optionally substituted with one or more C _1-12 alkyl groups.

在一些實施例中，供體為交替共聚物，其包含彼此直接結合的交替之供電子重複單元及受電子重複單元。In some embodiments, the donor is an alternating copolymer comprising alternating electron donating repeat units and electron accepting repeat units directly bonded to each other.

在一些實施例中，供體包含藉由橋接單元彼此隔開的交替之供電子重複單元及受電子重複單元。較佳的橋接單元為視情況經取代之單環芳族或雜芳族單元，更佳為包含選自C以及S、O及N中之一者或多者之環原子的5員雜芳族單元，最佳為噻吩。橋接單元之C原子的取代基可選自如上文所述的非H基團R ²⁵。橋接單元之N原子的取代基可選自如上文所述的基團R ²³。 In some embodiments, the donor comprises alternating electron donating repeating units and electron accepting repeating units separated from each other by a bridging unit. Preferred bridging units are optionally substituted monocyclic aromatic or heteroaromatic units, more preferably 5-membered heteroaromatic units comprising ring atoms selected from C and one or more of S, O and N, most preferably thiophene. Substituents of the C atoms of the bridging unit may be selected from the non-H groups R ²⁵ as described above. Substituents of the N atoms of the bridging unit may be selected from the groups R ²³ as described above.

例示性供體材料揭示於例如WO2013/051676中，該文獻之內容以引用之方式併入本文中。Exemplary donor materials are disclosed, for example, in WO2013/051676, the contents of which are incorporated herein by reference.

在一些實施例中，共軛聚合物供體之形成包含式M-1單體與式M-2單體之聚合： LG1-A-LG1 LG2-D-LG2 M-1 M-2 其中： LG1為離去基，其選自以下中之一者：(a)鹵素或-OSO ₂R ⁸，其中R ⁸為視情況經取代之C1-12烷基或芳基及(b)硼酸或酯。 LG2為(a)及(b)中之另一者； A為用於形成受電子重複單元的基團；且 In some embodiments, the formation of the conjugated polymer donor comprises polymerization of a monomer of formula M-1 and a monomer of formula M-2: LG1-A-LG1 LG2-D-LG2 M-1 M-2 wherein: LG1 is a leaving group selected from one of the following: (a) a halogen or -OSO ₂ R ⁸ , wherein R ⁸ is an optionally substituted C1-12 alkyl or aryl group and (b) a boronic acid or ester. LG2 is the other of (a) and (b); A is a group for forming an electron accepting repeating unit; and

B為用於形成供電子重複單元的基團。B is a group for forming an electron-donating repeating unit.

R ⁸較佳為視情況經一個或多個F原子取代的C _1-12烷基或苯基。 ^R8 is preferably a _C1-12 alkyl group or a phenyl group which is optionally substituted by one or more F atoms.

在其他實施例中，M-1經式M-1'之單體置換，或M-2經式M-2'之單體置換，其中B為如本文所述的橋基： LG1-B-A-B-LG1 LG2-B-D-B- LG2 M-1' M-2' In other embodiments, M-1 is replaced by a monomer of the formula M-1', or M-2 is replaced by a monomer of the formula M-2', wherein B is a bridge group as described herein: LG1-B-A-B-LG1 LG2-B-D-B- LG2 M-1' M-2'

由式M-1單體之反應形成的例示性基團包括： Exemplary groups formed by reaction of monomers of formula M-1 include:

視情況，p型供體的HOMO能級距離真空能級不超過5.5 eV。視情況，p型供體的HOMO能級距離真空能級為至少4.1 eV。Optionally, the HOMO energy level of the p-type donor is no more than 5.5 eV away from the vacuum energy level. Optionally, the HOMO energy level of the p-type donor is at least 4.1 eV away from the vacuum energy level.

除非另有說明，否則如本文所述之化合物的HOMO及LUMO能級係使用方波伏安法、用化合物之膜量測。Unless otherwise stated, the HOMO and LUMO energy levels of compounds described herein were measured using square wave voltammetry with films of the compounds.

在一些實施例中，供體化合物相對於受體化合物之重量比為約1:0.5至約1:2。In some embodiments, the weight ratio of the donor compound to the acceptor compound is about 1:0.5 to about 1:2.

較佳地，供體化合物相對於受體化合物的重量比為約1:1或約1:1.5。Preferably, the weight ratio of the donor compound to the acceptor compound is about 1:1 or about 1:1.5.

第一電極及第二電極中之至少一者為透明的，使得入射於裝置上之光可到達本體異質接面層。在一些實施例中，第一電極與第二電極均為透明的。At least one of the first electrode and the second electrode is transparent so that light incident on the device can reach the bulk heterojunction layer. In some embodiments, both the first electrode and the second electrode are transparent.

各透明電極對300至900 nm範圍內的波長較佳具有至少70%，視情況至少80%之透射率。Each transparent electrode preferably has a transmittance of at least 70%, and optionally at least 80%, for wavelengths in the range of 300 to 900 nm.

在一些實施例中，一個電極為透明的且另一電極為反射性的。In some embodiments, one electrode is transparent and the other electrode is reflective.

視情況，透明電極包含或由透明導電氧化物(較佳為氧化銦錫或氧化銦鋅)層組成。在較佳實施例中，電極可包含聚3,4-伸乙二氧基噻吩(PEDOT)。在其他較佳實施例中，電極可包含PEDOT與聚苯乙烯磺酸酯(PSS)之混合物。電極可由PEDOT:PSS層組成。Optionally, the transparent electrode comprises or consists of a transparent conductive oxide (preferably indium tin oxide or indium zinc oxide) layer. In a preferred embodiment, the electrode may comprise poly (3,4-ethylenedioxythiophene) (PEDOT). In other preferred embodiments, the electrode may comprise a mixture of PEDOT and polystyrene sulfonate (PSS). The electrode may consist of a PEDOT:PSS layer.

視情況，反射電極可包含反射金屬層。反射材料層可為鋁或銀或金。在一些實施例中，可使用雙層電極。舉例而言，電極可為氧化銦錫(ITO)/銀雙層、ITO/鋁雙層或ITO/金雙層。Optionally, the reflective electrode may include a reflective metal layer. The reflective material layer may be aluminum or silver or gold. In some embodiments, a double-layer electrode may be used. For example, the electrode may be an indium tin oxide (ITO)/silver double layer, an ITO/aluminum double layer, or an ITO/gold double layer.

裝置可如下形成：在基板所支撐之陽極及陰極中之一者上形成本體異質接面層以及在該本體異質接面層上沈積陽極或陰極中之另一者。The device may be formed by forming a bulk heterojunction layer on one of the anode and cathode supported by a substrate and depositing the other of the anode or cathode on the bulk heterojunction layer.

OPD面積可小於約3 cm ²、小於約2 cm ²、小於約1 cm ²、小於約0.75 cm ²、小於約0.5 cm ²或小於約0.25 cm ²。基板可為(不限於)玻璃或塑膠基板。基板可描述為無機半導體。在一些實施例中，基板可為矽。舉例而言，基板可為矽晶圓。在使用時，若入射光透射穿過基板且電極由基板支撐，則基板為透明的。 The OPD area may be less than about 3 cm ² , less than about 2 cm ² , less than about 1 cm ² , less than about 0.75 cm ² , less than about 0.5 cm ² , or less than about 0.25 cm ² . The substrate may be, without limitation, a glass or plastic substrate. The substrate may be described as an inorganic semiconductor. In some embodiments, the substrate may be silicon. For example, the substrate may be a silicon wafer. In use, the substrate is transparent if incident light is transmitted through the substrate and the electrodes are supported by the substrate.

在使用時，若入射光透射穿過陽極及陰極中之另一者，則支撐陽極及陰極中之一者的基板可為或可不為透明的。In use, the substrate supporting one of the anode and cathode may or may not be transparent if incident light is transmitted through the other of the anode and cathode.

本體異質接面層可藉由包括但不限於熱蒸發及溶液沈積法之任何製程來形成。The bulk heterojunction layer may be formed by any process including but not limited to thermal evaporation and solution deposition.

較佳地，本體異質接面層係藉由沈積調配物來形成，該調配物包含溶解於或分散於溶劑或兩種或更多種溶劑之混合物中的受體材料及電子供體材料。調配物可藉由包括但不限於以下之任何塗佈或印刷方法來沈積：旋塗、浸塗、滾塗、噴塗、刮刀塗佈、線棒塗佈、狹縫塗佈、噴墨印刷、網版印刷、凹版印刷及柔版印刷。Preferably, the bulk heterojunction layer is formed by depositing a formulation comprising an acceptor material and an electron donor material dissolved or dispersed in a solvent or a mixture of two or more solvents. The formulation can be deposited by any coating or printing method including but not limited to spin coating, dip coating, roll coating, spray coating, doctor blade coating, wire bar coating, slit coating, inkjet printing, screen printing, gravure printing, and flexographic printing.

調配物中的一種或多種溶劑可視情況包含以下或由以下組成：經一個或多個選自氯、C _1-10烷基及C _1-10烷氧基之取代基取代的苯，其中兩個或更多個取代基可連接以形成可未取代或經一個或多個C _1-6烷基取代之環，視情況為甲苯、二甲苯、三甲苯、四甲苯、茴香醚、二氫茚及其經烷基取代之衍生物，以及四氫萘及其經烷基取代之衍生物。 The one or more solvents in the formulation may optionally comprise or consist of benzene substituted with one or more substituents selected from chlorine, _C1-10 alkyl and _C1-10 alkoxy, wherein two or more substituents may be linked to form a ring which may be unsubstituted or substituted with one or more _C1-6 alkyl, optionally toluene, xylene, mesitylene, tetramethylbenzene, anisole, dihydroindene and alkyl-substituted derivatives thereof, and tetrahydronaphthalene and alkyl-substituted derivatives thereof.

調配物可包含兩種或更多種溶劑之混合物，較佳為包含至少一種經一個或多個如上文所述之取代基取代之苯及一種或多種其他溶劑的混合物。一種或多種其他溶劑可選自酯，視情況為烷基或芳基羧酸之烷基酯或芳基酯，視情況為苯甲酸C _1-10烷酯、苯甲酸苯甲酯或二甲氧基苯。在較佳實施例中，三甲苯與苯甲酸苯甲酯之混合物用作溶劑。在其他較佳實施例中，三甲苯與二甲氧基苯之混合物用作溶劑。 The formulation may comprise a mixture of two or more solvents, preferably a mixture comprising at least one benzene substituted with one or more substituents as described above and one or more other solvents. The one or more other solvents may be selected from esters, optionally alkyl or aryl esters of alkyl or aryl carboxylic acids, optionally C _1-10 alkyl benzoates, benzyl benzoate or dimethoxybenzene. In a preferred embodiment, a mixture of trimethylbenzene and benzyl benzoate is used as a solvent. In other preferred embodiments, a mixture of trimethylbenzene and dimethoxybenzene is used as a solvent.

除電子受體、電子供體及一種或多種溶劑以外，調配物亦可包含其他組分。作為此類組分之實例，可提及黏著劑、消泡劑、除氣劑、黏度增強劑、稀釋劑、助劑、流動改良劑、著色劑、染料或顏料、敏化劑、穩定劑、奈米粒子、表面活性化合物、潤滑劑、濕潤劑、分散劑及抑制劑。In addition to the electron acceptor, the electron donor and one or more solvents, the formulation may also contain other components. As examples of such components, there may be mentioned adhesives, defoamers, deaerators, viscosity enhancers, diluents, adjuvants, flow improvers, colorants, dyes or pigments, sensitizers, stabilizers, nanoparticles, surface-active compounds, lubricants, wetting agents, dispersants and inhibitors.

如本文所述之有機光偵測器可用於廣泛範圍的應用中，包括但不限於偵測環境光之存在及/或亮度；及用於包含有機光偵測器及光源之感測器中。光偵測器可經組態以使得自光源發射之光入射於光偵測器上，且可偵測光波長及/或亮度的變化，例如歸因於光源與有機光偵測器之間之光路中所安置之樣品中之目標材料的吸收及/或發射光。感測器可為(不限於)氣體感測器、生物感測器、X射線成像裝置、影像感測器(諸如相機影像感測器)、運動感測器(例如用於安全應用中)、近接感測器或指紋感測器。1D或2D光感測器陣列可包含影像感測器中之複數個如本文所述的光偵測器。光偵測器可經組態以偵測自目標分析物發射的光，該目標分析物在光源照射後發射光，或偵測與冷光標籤結合之目標分析物所發射的光，該冷光標籤在光源照射後發射光。光偵測器可經組態以偵測由目標分析物或與其結合之冷光標籤發射之光的波長。實例合成 Organic photodetectors as described herein may be used in a wide range of applications, including, but not limited to, detecting the presence and/or brightness of ambient light; and in sensors comprising an organic photodetector and a light source. The photodetector may be configured such that light emitted from the light source is incident on the photodetector, and changes in the wavelength and/or brightness of the light may be detected, for example due to absorption and/or emission of light by a target material in a sample disposed in the light path between the light source and the organic photodetector. The sensor may be, but is not limited to, a gas sensor, a biosensor, an X-ray imaging device, an image sensor (such as a camera image sensor), a motion sensor (e.g., for use in security applications), a proximity sensor, or a fingerprint sensor. A 1D or 2D photosensor array may include a plurality of photodetectors as described herein in an imaging sensor. The photodetector may be configured to detect light emitted from a target analyte that emits light upon illumination by a light source, or to detect light emitted by a target analyte bound to a luminescent tag that emits light upon illumination by a light source. The photodetector may be configured to detect the wavelength of light emitted by the target analyte or a luminescent tag bound thereto. Example Synthesis

化合物可根據以下反應流程製備： The compounds can be prepared according to the following reaction scheme:

化合物實例1係根據以下反應流程製備：階段1 Compound Example 1 was prepared according to the following reaction scheme: Phase 1

將醛(3 g，9.4 mmol)溶解於氯仿(30 mL)及吡啶(5 mL)中。將溶液除氣0.5小時且接著冷卻至0℃。添加二氟單元(3.2 g，15.5 mmol)且將反應混合物再除氣0.25小時且接著升溫至室溫維持3小時。添加甲醇且移除溶劑以產生紅色固體。此粗物質在二氧化矽上用石油醚:DCM 9:1溶離、藉由管柱層析加以純化。將含產物之溶離份濃縮，產生具有98%純度的階段1物質(3.5 g)。階段2 The aldehyde (3 g, 9.4 mmol) was dissolved in chloroform (30 mL) and pyridine (5 mL). The solution was degassed for 0.5 h and then cooled to 0 °C. Difluoromonomer (3.2 g, 15.5 mmol) was added and the reaction mixture was degassed for another 0.25 h and then warmed to room temperature for 3 h. Methanol was added and the solvent was removed to produce a red solid. The crude material was purified by column chromatography on silica eluted with petroleum ether:DCM 9:1. The fraction containing the product was concentrated to produce stage 1 material (3.5 g) with 98% purity. Stage 2

將稠合的噻吩物質(其可如以下文獻中製得： Macromolecular Rapid Communications, 2011, 32, 1664或Chem. Mater., 2017, 29, 8369)(1 g，1.0 mmol)溶解於THF中且在氮氣下冷卻至-78℃。逐滴添加正丁基鋰(1.65 mL，4.1 mmol)且在-78℃下攪拌溶液1小時，隨後逐滴添加含有氯化三丁基錫(0.99 mg，3.0 mmol)之THF (5 mL)。允許反應混合物經16小時達到室溫。添加甲醇以淬滅反應物且移除溶劑。粗物質用甲醇濕磨若干次，產生階段2物質，其未經進一步純化即用於下一步驟中。化合物實例1 The fused thiophene material (which can be prepared as in the following references: Macromolecular Rapid Communications , 2011, 32, 1664 or Chem. Mater., 2017, 29, 8369) (1 g, 1.0 mmol) was dissolved in THF and cooled to -78 °C under nitrogen. n-Butyl lithium (1.65 mL, 4.1 mmol) was added dropwise and the solution was stirred at -78 °C for 1 hour, followed by the dropwise addition of THF (5 mL) containing tributyltin chloride (0.99 mg, 3.0 mmol). The reaction mixture was allowed to reach room temperature over 16 hours. Methanol was added to quench the reaction and the solvent was removed. The crude material was triturated several times with methanol to produce stage 2 material, which was used in the next step without further purification. Compound Example 1

將階段1物質(1.3 g，2.4 mmol)及階段2物質(1.5 g，0.97 mmol)溶解於甲苯中且除氣。添加三(鄰甲苯基)膦(88 mg，0.3 mmol)及參(二苯亞甲基丙酮)二鈀(71 mg，0.08 mmol)且在80℃下攪拌反應混合物5小時。使反應混合物冷卻且使其通過矽藻土塞，進一步用甲苯溶離。濃縮濾液，得到黑色半固體，用甲醇濕磨，得到呈固體狀之粗產物。此產物在二氧化矽上使用DCM/己烷、藉由管柱層析加以純化。濃縮含產物溶離份，得到具有97.8%純度之呈黑色固體狀之產物(530 mg)。化合物實例2 Stage 1 material (1.3 g, 2.4 mmol) and Stage 2 material (1.5 g, 0.97 mmol) were dissolved in toluene and degassed. Tri(o-tolyl)phosphine (88 mg, 0.3 mmol) and dipalladium tris(benzylideneacetone) (71 mg, 0.08 mmol) were added and the reaction mixture was stirred at 80 °C for 5 hours. The reaction mixture was cooled and passed through a plug of celite and further dissolved with toluene. The filtrate was concentrated to give a black semisolid which was triturated with methanol to give the crude product as a solid. This product was purified by column chromatography on silica using DCM/hexanes. The product-containing fraction was concentrated to obtain a black solid product (530 mg) with a purity of 97.8%. Compound Example 2

化合物實例2係根據以下反應流程製備：中間物2： Compound Example 2 was prepared according to the following reaction scheme: Intermediate 2:

在-78℃下將正丁基鋰(97.4 ml，1.6 M，0.16 mol)添加至噻吩并[3,2-b]噻吩(1)(10 g，0.07 mol)於THF (100 ml)中之溶液中且在25℃下攪拌混合物一小時。冷卻至-78℃之後，添加含有氯化三甲基錫(35.5 g，0.18 mol)之THF (100 ml)且在25℃下攪拌混合物16小時。其接著在0℃下用水(200 ml)淬滅，用己烷(200 ml)萃取，有機層用鹽水洗滌且經無水硫酸鈉乾燥且濃縮。將粗固體溶解於氯仿(50 ml)中，添加甲醇(250 ml)且在0℃下攪拌混合物2小時。過濾所得漿液，用甲醇(100 ml)洗滌且真空乾燥，得到呈白色固體狀的中間物2 (20 g，60%產率)。 HPLC:98.45%。 ¹H-NMR (400 MHz, DMSO-d ₆):δ [ppm]0.362 (s, 18H), 7.38 (s, 2H)。中間物4： n-Butyl lithium (97.4 ml, 1.6 M, 0.16 mol) was added to a solution of thieno[3,2-b]thiophene (1) (10 g, 0.07 mol) in THF (100 ml) at -78°C and the mixture was stirred at 25°C for one hour. After cooling to -78°C, THF (100 ml) containing trimethyltin chloride (35.5 g, 0.18 mol) was added and the mixture was stirred at 25°C for 16 hours. It was then quenched with water (200 ml) at 0°C, extracted with hexane (200 ml), the organic layer was washed with brine and dried over anhydrous sodium sulfate and concentrated. The crude solid was dissolved in chloroform (50 ml), methanol (250 ml) was added and the mixture was stirred at 0°C for 2 hours. The resulting slurry was filtered, washed with methanol (100 ml) and dried in vacuo to afford Intermediate 2 (20 g, 60% yield) as a white solid. HPLC: 98.45%. ¹ H-NMR (400 MHz, DMSO-d ₆ ): δ [ppm] 0.362 (s, 18H), 7.38 (s, 2H). Intermediate 4:

中間物3可如以下文獻中所述合成：Journal of Materials Chemistry A: Materials for Energy and Sustainability (2020), 8, (10), 5163-5170，該文獻之內容以引用的方式併入本文中。Intermediate 3 can be synthesized as described in the following reference: Journal of Materials Chemistry A: Materials for Energy and Sustainability (2020), 8, (10), 5163-5170, the contents of which are incorporated herein by reference.

將雙(三苯膦)二氯化鈀(II)(144 mg，0.2 mmol)添加至中間物2 (4.8 g，0.01 mol)與2-溴噻吩-3-甲酸甲酯(3)(4.77 g，0.02 mmol)於除氣之甲苯(100 ml)中之混合物中且在80℃下加熱混合物16小時。冷卻後，過濾所得漿液，用甲苯(20 ml)洗滌且真空乾燥，得到呈黃色固體狀的中間物4 (4.5 g)。 HPLC:95.7%。 ¹H-NMR (400 MHz, CDCl ₃):δ [ppm]1.57 (s, 4H), 3.88 (s, 6H), 7.28 (s, 2H), 7.54 (d, J= 5.40 Hz, 2H), 7.69 (s, 2H)。中間物6： Bis(triphenylphosphine)palladium(II) dichloride (144 mg, 0.2 mmol) was added to a mixture of intermediate 2 (4.8 g, 0.01 mol) and methyl 2-bromothiophene-3-carboxylate (3) (4.77 g, 0.02 mmol) in degassed toluene (100 ml) and the mixture was heated at 80°C for 16 hours. After cooling, the resulting slurry was filtered, washed with toluene (20 ml) and dried in vacuo to give intermediate 4 (4.5 g) as a yellow solid. HPLC: 95.7%. ¹ H-NMR (400 MHz, CDCl ₃ ):δ [ppm]1.57 (s, 4H), 3.88 (s, 6H), 7.28 (s, 2H), 7.54 (d, J = 5.40 Hz, 2H), 7.69 (s, 2H). Intermediate 6:

在-100℃下，將正丁基鋰(2.5 M於己烷中，17.1 ml，0.04 mol)添加至1-溴-4-己基苯(5)(12.0 g，0.05 mol)於THF (60 ml)中之溶液中且攪拌混合物2.5小時。中間物4 (3 g，0.01 mol)作為固體添加且將混合物升溫至25℃且攪拌16小時。冷卻至0℃後，將其用NH ₄Cl溶液(20%水溶液，30 ml)淬滅，用乙酸乙酯(2×20 ml)萃取，用鹽水(30 ml)洗滌，經無水硫酸鈉乾燥且在減壓下濃縮。藉由二氧化矽管柱層析(2% EtOAc/己烷作為溶離劑)純化殘餘物，得到中間物6 (4.5 g，63%產率)。 LCMS:96.5%。 ¹H-NMR (400 MHz, CDCl ₃):δ [ppm]0.91 (t, J= 6.64 Hz, 12H), 1.33-1.37 (m, 24H), 1.59-1.64 (m, 8H), 2.62 (t, J= 7.88 Hz, 8H), 3.26(bs, 2H), 6.47 (d, J= 5.36 Hz, 2H), 6.66 (s, 2H), 7.11-7.17 (m, 18H)。中間物7： n-Butyl lithium (2.5 M in hexane, 17.1 ml, 0.04 mol) was added to a solution of 1-bromo-4-hexylbenzene (5) (12.0 g, 0.05 mol) in THF (60 ml) at -100°C and the mixture was stirred for 2.5 hours. Intermediate 4 (3 g, 0.01 mol) was added as a solid and the mixture was warmed to 25°C and stirred for 16 hours. After cooling to 0°C, it was quenched with _NH4Cl solution (20% aqueous solution, 30 ml), extracted with ethyl acetate (2 x 20 ml), washed with brine (30 ml), dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was purified by silica column chromatography (2% EtOAc/hexane as solvent) to give intermediate 6 (4.5 g, 63% yield). LCMS: 96.5%. ¹ H-NMR (400 MHz, CDCl ₃ ): δ [ppm] 0.91 (t, J = 6.64 Hz, 12H), 1.33-1.37 (m, 24H), 1.59-1.64 (m, 8H), 2.62 (t, J = 7.88 Hz, 8H), 3.26 (bs, 2H), 6.47 (d, J = 5.36 Hz, 2H), 6.66 (s, 2H), 7.11-7.17 (m, 18H). Intermediate 7:

在0℃下，在氮氣下，將三氟化硼合二***(2.74 ml，0.02 mol)逐滴添加至中間物(6)(4.5 g，0.004 mol)於無水DCM (60 ml)中之溶液中。在26℃下攪拌16小時之後，混合物用冰水(30 ml)淬滅，用二氯甲烷(50 ml)稀釋，有機層用水(30 ml)洗滌，經無水硫酸鈉乾燥且在減壓下濃縮。藉由二氧化矽管柱層析(2至5% DCM/己烷作為溶離劑)純化殘餘物，得到呈橙紅色固體狀之中間物7 (2 g，46%產率)。 HPLC:98.1%。 ¹H-NMR (400 MHz, CDCl ₃): δ [ppm]0.88 (t, J= 6.84 Hz, 12H), 1.29-1.37 (m, 24H), 1.55-1.63 (m, 8H), 2.56 (t, J= 7.92 Hz, 8H), 7.08-7.10 (m, 10H), 7.16-7.18 (m, 10H)。中間物8： Boron trifluoride diethyl etherate (2.74 ml, 0.02 mol) was added dropwise to a solution of intermediate (6) (4.5 g, 0.004 mol) in anhydrous DCM (60 ml) at 0°C under nitrogen. After stirring at 26°C for 16 hours, the mixture was quenched with ice water (30 ml), diluted with dichloromethane (50 ml), the organic layer was washed with water (30 ml), dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was purified by silica column chromatography (2 to 5% DCM/hexane as solvent) to give intermediate 7 (2 g, 46% yield) as an orange-red solid. HPLC: 98.1%. ¹ H-NMR (400 MHz, CDCl ₃ ): δ [ppm] 0.88 (t, J = 6.84 Hz, 12H), 1.29-1.37 (m, 24H), 1.55-1.63 (m, 8H), 2.56 (t, J = 7.92 Hz, 8H), 7.08-7.10 (m, 10H), 7.16-7.18 (m, 10H). Intermediate 8:

在-78℃下，將正丁基鋰(2.5 M於己烷中，16.5 ml，0.04 mol)添加至中間物7 (10 g，0.01 mol)於無水THF (150 ml)中之溶液中。1小時之後，緩慢添加含氯化三丁基錫(16.9 g，0.05 mol)之THF (20 ml)且將混合物升溫至室溫且攪拌16小時。在減壓下移除溶劑且粗殘餘物用甲醇濕磨且過濾，得到呈黃色固體狀之中間物8 (4 g，約75%所需產物，根據LCMS)。中間物10： n-Butyl lithium (2.5 M in hexane, 16.5 ml, 0.04 mol) was added to a solution of intermediate 7 (10 g, 0.01 mol) in anhydrous THF (150 ml) at -78 °C. After 1 hour, tributyltin chloride (16.9 g, 0.05 mol) in THF (20 ml) was slowly added and the mixture was warmed to room temperature and stirred for 16 hours. The solvent was removed under reduced pressure and the crude residue was triturated with methanol and filtered to give intermediate 8 (4 g, about 75% desired product by LCMS) as a yellow solid. Intermediate 10:

將三(鄰甲苯基)膦(147 mg，0.48 mmol)及參(二苯亞甲基丙酮)-二鈀(0)(117 mg，0.13 mmol)添加至中間物8 (2.5 g，1.61 mmol)及5-溴-4-[(2-乙基己基)氧基]噻吩-2-甲醛(1.28 g，4.02 mmol)於甲苯(150 ml)中之經除氣之溶液中且將混合物加熱至80℃維持16小時。濃縮混合物且藉由二氧化矽管柱層析(0至50% DCM/己烷作為溶離劑)純化粗產物，得到中間物10 (1.1 g，LCMS純度81%；及0.3 g，LCMS純度86%)。化合物實例2： Tri(o-tolyl)phosphine (147 mg, 0.48 mmol) and tris(dibenzylideneacetone)-dipalladium(0) (117 mg, 0.13 mmol) were added to a degassed solution of intermediate 8 (2.5 g, 1.61 mmol) and 5-bromo-4-[(2-ethylhexyl)oxy]thiophene-2-carbaldehyde (1.28 g, 4.02 mmol) in toluene (150 ml) and the mixture was heated to 80°C for 16 hours. The mixture was concentrated and the crude product was purified by silica column chromatography (0 to 50% DCM/hexane as solvent) to give intermediate 10 (1.1 g, LCMS purity 81%; and 0.3 g, LCMS purity 86%). Compound Example 2:

中間物10 (550 mg，0.38 mmol)、中間物11 (461 mg，1.89 mmol)及對甲苯磺酸(540 mg，2.84 mmol)於乙醇(25 ml)中之經除氣之溶液在65℃下攪拌18小時且濃縮混合物。亦將另外550 mg中間物10轉化為化合物實例1。合併粗產物且藉由二氧化矽管柱層析(己烷:二氯甲烷(1:1)作為溶離劑)純化兩次。將含有所需產物之溶離份合併且進一步用乙醇濕磨且過濾，得到化合物實例2 (500 mg)。 HPLC:93.79%。 ¹H-NMR (400 MHz, CDCl ₃): δ [ppm]0.87-0.90 (m, 12H), 0.93-0.97 (m, 6H), 0.99-1.04 (m, 6H), 1.29-1.34 (m, 12H), 1.26-1.41 (m, 12H), 1.56-1.67 (m, 24H), 1.85-1.90 (m, 2H), 2.61 (t, J= 7.6 Hz, 8H), 4.17 (d, J= 4.8 Hz, 4H), 7.15-7.20 (m, 18H), 7.78 (s, 2H), 8.12 (s, 2H), 8.75 (br, s, 2H), 8.98 (s, 2H)。 A degassed solution of intermediate 10 (550 mg, 0.38 mmol), intermediate 11 (461 mg, 1.89 mmol) and p-toluenesulfonic acid (540 mg, 2.84 mmol) in ethanol (25 ml) was stirred at 65° C. for 18 hours and the mixture was concentrated. Another 550 mg of intermediate 10 was also converted into compound example 1. The crude products were combined and purified twice by silica column chromatography (hexane: dichloromethane (1:1) as solvent). The fractions containing the desired product were combined and further triturated with ethanol and filtered to give compound example 2 (500 mg). HPLC: 93.79%. ¹ H-NMR (400 MHz, CDCl ₃ ): δ [ppm] 0.87-0.90 (m, 12H), 0.93-0.97 (m, 6H), 0.99-1.04 (m, 6H), 1.29-1.34 (m, 12H), 1.26-1.41 (m, 12H), 1.56-1.67 (m, 24H), 1.85-1.90 (m, 2H), 2.61 (t, J = 7.6 Hz, 8H), 4.17 (d, J = 4.8 Hz, 4H), 7.15-7.20 (m, 18H), 7.78 (s, 2H), 8.12 (s, 2H), 8.75 (br, s, 2H), 8.98 (s, 2H).

中間物11係根據以下反應流程形成：中間物13 Intermediate 11 is formed according to the following reaction process: Intermediate 13

1,2-二溴-4,5-二甲苯(100 g，0.38 mol)、氫氧化鉀(105 g，1.89 mol)及高錳酸鉀(298 g，1.89 mol)於水(2 L)中之混合物在115℃下加熱24小時。冷卻至室溫後，添加亞硫酸氫鈉，使用10%氫氧化鉀溶液將pH調節至8，且經由矽藻土墊過濾混合物且用水(2×50 ml)洗滌。水層用濃HCl酸化至pH 1，得到白色沈澱物，過濾，用水(2×250 ml)洗滌且用甲醇濕磨。過濾所得固體且真空乾燥，得到中間物13 (46 g，38%產率)。 ¹H-NMR (400 MHz, DMSO-d6): δ [ppm]8.18 (s, 2H)。中間物14： A mixture of 1,2-dibromo-4,5-dimethylbenzene (100 g, 0.38 mol), potassium hydroxide (105 g, 1.89 mol) and potassium permanganate (298 g, 1.89 mol) in water (2 L) was heated at 115 °C for 24 h. After cooling to room temperature, sodium bisulfite was added, the pH was adjusted to 8 using 10% potassium hydroxide solution, and the mixture was filtered through a diatomaceous earth pad and washed with water (2×50 ml). The aqueous layer was acidified to pH 1 with concentrated HCl to give a white precipitate, which was filtered, washed with water (2×250 ml) and triturated with methanol. The resulting solid was filtered and dried in vacuo to give intermediate 13 (46 g, 38% yield). ¹ H-NMR (400 MHz, DMSO-d6): δ [ppm] 8.18 (s, 2H). Intermediate 14:

將乙酸酐(I L)中之中間物13 (200 g，618 mmol)在130℃下加熱4小時。冷卻至室溫後，過濾粗固體，用甲苯(200 ml)洗滌且在真空下乾燥，得到中間物14 (200 g)。中間物15： Intermediate 13 (200 g, 618 mmol) in acetic anhydride (1 L) was heated at 130 °C for 4 h. After cooling to room temperature, the crude solid was filtered, washed with toluene (200 ml) and dried under vacuum to give intermediate 14 (200 g). Intermediate 15:

將乙醯乙酸三級丁酯(103 g，654 mmol)添加至中間物14 (200 g，654 mmol)、乙酸酐(1 L)及三乙胺(600 ml)之混合物中且在25℃下攪拌反應混合物16小時。在維持溫度低於50℃的同時用(10 M HCl，1 L)與冰(1 kg)之混合物淬滅之後，將混合物加熱至75℃維持2小時且冷卻至室溫。過濾固體且乾燥，得到呈棕色固體狀之中間物15 (132 g，68%產率)。 LCMS:96.8%。 ¹H-NMR (400 MHz, DMSO-d6): δ [ppm]3.28 (s, 2H), 8.25 (s, 2H)。中間物16： Tributyl acetoacetate (103 g, 654 mmol) was added to a mixture of intermediate 14 (200 g, 654 mmol), acetic anhydride (1 L) and triethylamine (600 ml) and the reaction mixture was stirred at 25°C for 16 hours. After quenching with a mixture of (10 M HCl, 1 L) and ice (1 kg) while maintaining the temperature below 50°C, the mixture was heated to 75°C for 2 hours and cooled to room temperature. The solid was filtered and dried to give intermediate 15 (132 g, 68% yield) as a brown solid. LCMS: 96.8%. ¹ H-NMR (400 MHz, DMSO-d6): δ [ppm] 3.28 (s, 2H), 8.25 (s, 2H). Intermediate 16:

中間物15 (120 g，394 mmol)、乙二醇(244 g，3.9 mol)及對甲苯磺酸(6.78 g，39.4 mmol)於甲苯(1.5 L)中之溶液在125℃下加熱40小時。冷卻至室溫後，將反應混合物添加至水(500 ml)中，分離有機層且在真空下濃縮。將粗殘餘物懸浮於己烷(1 L)中，攪拌30分鐘且過濾，得到中間物16 (91 g，59%產率)。 ¹H-NMR (400 MHz, CDCl3): δ [ppm]2.56 (s, 2H), 4.09 - 4.12 (m, 4H), 4.20 - 4.24 (m, 4H), 7.65 (s, 2H)。中間物17： A solution of intermediate 15 (120 g, 394 mmol), ethylene glycol (244 g, 3.9 mol) and p-toluenesulfonic acid (6.78 g, 39.4 mmol) in toluene (1.5 L) was heated at 125 °C for 40 hours. After cooling to room temperature, the reaction mixture was added to water (500 ml), the organic layer was separated and concentrated under vacuum. The crude residue was suspended in hexane (1 L), stirred for 30 minutes and filtered to give intermediate 16 (91 g, 59% yield). ¹ H-NMR (400 MHz, CDCl3): δ [ppm] 2.56 (s, 2H), 4.09 - 4.12 (m, 4H), 4.20 - 4.24 (m, 4H), 7.65 (s, 2H). Intermediate 17:

將亞鐵氰化鉀(48.6 g，132 mmol)、1-丁基咪唑(42.9 g，383 mmol)及碘化亞銅(I)(12.5 g，65.6 mmol)分三份添加至中間物16 (65 g，165 mmol)於鄰二甲苯(2.5 L)中之溶液中。在140℃下加熱44小時之後，將反應混合物冷卻至室溫，經由Florisil塞過濾，且用甲苯洗滌，隨後用乙酸乙酯洗滌。在減壓下濃縮濾液至1 L且在25℃下攪拌16小時。過濾所得固體，用己烷洗滌且藉由二氧化矽管柱層析(己烷:乙酸乙酯(2:8)作為溶離劑)純化。在減壓下濃縮含有所需產物之溶離份，將己烷(1 L)添加至殘餘物中，且過濾所得固體且在真空下乾燥，得到中間物17 (30 g，64%產率)。 HPLC:98.9%。 ¹H-NMR (400 MHz, CDCl3): δ [ppm]2.62 (s, 2H), 4.15 - 4.21 (m, 4H), 4.24 - 4.28 (m, 4H), 7.83 (s, 2H)。中間物18： Potassium ferrocyanide (48.6 g, 132 mmol), 1-butylimidazole (42.9 g, 383 mmol) and cuprous (I) iodide (12.5 g, 65.6 mmol) were added in three portions to a solution of intermediate 16 (65 g, 165 mmol) in o-xylene (2.5 L). After heating at 140° C. for 44 hours, the reaction mixture was cooled to room temperature, filtered through a Florisil plug, and washed with toluene and then with ethyl acetate. The filtrate was concentrated to 1 L under reduced pressure and stirred at 25° C. for 16 hours. The obtained solid was filtered, washed with hexane and purified by silica column chromatography (hexane:ethyl acetate (2:8) as solvent). The fraction containing the desired product was concentrated under reduced pressure, hexane (1 L) was added to the residue, and the obtained solid was filtered and dried under vacuum to give intermediate 17 (30 g, 64% yield). HPLC: 98.9%. ¹ H-NMR (400 MHz, CDCl3): δ [ppm] 2.62 (s, 2H), 4.15 - 4.21 (m, 4H), 4.24 - 4.28 (m, 4H), 7.83 (s, 2H). Intermediate 18:

將含有氯化氫的***(2 M，500 ml，1.0 mol)及水(5 ml)添加至中間物17 (90 g，316 mmol)於第三丁基甲基醚(1 L)中之溶液中。在25℃下攪拌48小時之後，過濾混合物，所得固體用***(100 mL×3)洗滌且與丙酮(500 ml)一起攪拌3次，歷時1小時，且過濾。所得固體在真空下乾燥，得到中間物18 (61 g，80%產率)。 HPLC:95%。 1H-NMR (400 MHz, CDCl3): δ [ppm]3.07 (s, 2H), 4.20 - 4.36 (m, 4H), 8.11 (s, 1H), 8.16 (s, 1H)。中間物11 Diethyl ether (2 M, 500 ml, 1.0 mol) and water (5 ml) containing hydrogen chloride were added to a solution of intermediate 17 (90 g, 316 mmol) in tert-butyl methyl ether (1 L). After stirring at 25°C for 48 hours, the mixture was filtered, and the resulting solid was washed with diethyl ether (100 mL×3) and stirred with acetone (500 ml) 3 times for 1 hour and filtered. The resulting solid was dried under vacuum to give intermediate 18 (61 g, 80% yield). HPLC: 95%. 1H-NMR (400 MHz, CDCl3): δ [ppm] 3.07 (s, 2H), 4.20 - 4.36 (m, 4H), 8.11 (s, 1H), 8.16 (s, 1H). Intermediate 11

在25℃下將丙二腈(5.49 g，83.2 mmol)於THF (200 ml)中之溶液添加至氫化鈉(3.31 g，83.2 mmol)於THF (200 ml)中之懸浮液中且在25℃下攪拌一小時。所得混合物在0℃下添加至中間物18 (20 g，83.2 mmol)於THF (600 mL)中之懸浮液中，且在25℃下攪拌反應混合物16小時。所得混合物在真空下濃縮，得到深紫色粗固體。對另外40 g中間物18重複此程序。合併粗物質且藉由二氧化矽管柱層析(10至20% MeOH/DCM作為溶離劑)純化。合併含有所需產物之溶離份，在減壓下濃縮，且殘餘物在二氯甲烷與乙腈之混合物中攪拌，得到中間物11 (20.2 g，33%產率)。 LCMS:96.35%純度。 ¹H-NMR (400 MHz, CD3OD): δ [ppm]3.61 (s, 2H), 5.55 (s, 1H), 7.73 (s, 1H), 8.29 (s, 1H)。化合物實例3 A solution of malononitrile (5.49 g, 83.2 mmol) in THF (200 ml) was added to a suspension of sodium hydride (3.31 g, 83.2 mmol) in THF (200 ml) at 25°C and stirred at 25°C for one hour. The resulting mixture was added to a suspension of intermediate 18 (20 g, 83.2 mmol) in THF (600 mL) at 0°C, and the reaction mixture was stirred at 25°C for 16 hours. The resulting mixture was concentrated under vacuum to give a dark purple crude solid. This procedure was repeated for another 40 g of intermediate 18. The crude materials were combined and purified by silica column chromatography (10 to 20% MeOH/DCM as solvent). The fractions containing the desired product were combined, concentrated under reduced pressure, and the residue was stirred in a mixture of dichloromethane and acetonitrile to give intermediate 11 (20.2 g, 33% yield). LCMS: 96.35% purity. ¹ H-NMR (400 MHz, CD3OD): δ [ppm] 3.61 (s, 2H), 5.55 (s, 1H), 7.73 (s, 1H), 8.29 (s, 1H). Compound Example 3

化合物實例3可根據流程3製備：流程3 Compound Example 3 can be prepared according to Scheme 3: Process 3

中間物20可如以下文獻中所述合成： Adv. Sci.2018, 5, 1800307，該文獻之內容以引用的方式併入本文中。模型化資料 Intermediate 20 can be synthesized as described in the following document: Adv. Sci. 2018, 5, 1800307, the contents of which are incorporated herein by reference. Modeling Data

將以下化合物之LUMO能級及HOMO-LUMO帶隙模型化：模型化合物實例3 模型化合物實例4 模型化合物實例5 Model the LUMO energy levels and HOMO-LUMO band gaps of the following compounds: Model compound example 3 Model compound example 4 Model compound example 5

可使用獲自Gaussian的Gaussian09軟體、使用具有B3LYP (泛函)及LACVP* (基底函數組)的Gaussian09進行量子化學模型化。表1 化合物 HOMO (eV) LUMO (eV) 帶隙 (eV) 模型比較化合物1 -5.028 -3.262 1.767 模型比較化合物2 -5.129 -3.389 -1.740 模型化合物實例1 -4.839 -3.267 1.572 模型化合物實例2 -4.816 -3.235 1.580 模型比較化合物3 -5.375 -3.419 1.956 模型化合物實例3 -4.95 -3.41 1.54 模型化合物實例4 -5.28 -3.85 1.44 模型化合物實例5 -5.20 -3.80 1.40 The quantum chemical modeling can be performed using Gaussian09 software obtained from Gaussian using Gaussian09 with B3LYP (functional) and LACVP* (basis function set). Table 1 Compound HOMO (eV) LUMO (eV) Bandgap (eV) Model comparison compound 1 -5.028 -3.262 1.767 Model comparison compound 2 -5.129 -3.389 -1.740 Model compound example 1 -4.839 -3.267 1.572 Model compound example 2 -4.816 -3.235 1.580 Model comparison compound 3 -5.375 -3.419 1.956 Model compound example 3 -4.95 -3.41 1.54 Model compound example 4 -5.28 -3.85 1.44 Model compound example 5 -5.20 -3.80 1.40

參看表1，與模型比較化合物1或2相比，模型化合物實例1及2具有更淺(亦即，更接近於真空能級)的HOMO及更小的帶隙。 HOMO及LUMO量測 Referring to Table 1, model compound examples 1 and 2 have shallower (i.e., closer to the vacuum level) HOMO and smaller band gap than model comparison compound 1 or 2. HOMO and LUMO measurements

藉由方波伏安法量測化合物實例1之HOMO及LUMO值。The HOMO and LUMO values of Compound Example 1 were measured by square wave voltammetry.

在方波伏安法中，隨時間線性掃描工作電極與參考電極之間電位的同時，量測工作電極的電流。將正向脈衝與反向脈衝之間的差電流對電勢作圖以產生伏安圖。可使用CHI 660D恆電位器進行量測。In square wave voltammetry, the current at the working electrode is measured while the potential between the working electrode and the reference electrode is linearly scanned over time. The differential current between the forward pulse and the reverse pulse is plotted against the potential to produce a voltammogram. This can be measured using a CHI 660D potentiostat.

藉由SWV量測HOMO或LUMO能級之設備可包含：含有0.1 M六氟磷酸三級丁基銨於乙腈中的光析管；3 mm直徑玻璃態碳工作電極；鉑相對電極及無洩漏Ag/AgCl參考電極。The equipment for measuring HOMO or LUMO energy levels by SWV may include: a cuvette containing 0.1 M tributylammonium hexafluorophosphate in acetonitrile; a 3 mm diameter glassy carbon working electrode; a platinum counter electrode and a leak-free Ag/AgCl reference electrode.

在實驗結束時，將二茂鐵直接添加至現有光析管中用於計算目的，其中利用循環伏安法(CV)、針對二茂鐵相對於Ag/AgCl之氧化及還原來測定電位。At the end of the experiment, ferrocene was added directly to the existing cuvette for calculation purposes, where the potential was determined by cyclic voltammetry (CV) for the oxidation and reduction of ferrocene relative to Ag/AgCl.

將樣品溶解於甲苯(3 mg/ml)中，且直接在玻璃態碳工作電極上以3000 rpm旋轉。The samples were dissolved in toluene (3 mg/ml) and spun directly on a glassy carbon working electrode at 3000 rpm.

LUMO = 4.8-E二茂鐵(峰至峰平均值) - E樣品還原(峰最大值)。LUMO = 4.8 - E Ferrocene (peak to peak average) - E Sample reduced (peak maximum).

HOMO = 4.8-E二茂鐵(峰至峰平均值) + E樣品氧化(峰最大值)。HOMO = 4.8-E ferrocene (peak-to-peak average) + E sample oxidation (peak maximum).

典型的SWV實驗係在15 Hz頻率下運作；25 mV波幅及0.004 V增量步驟。根據HOMO與LUMO資料，計算出3個新近離心膜樣品的結果。表2 HOMO 膜(eV) LUMO 膜(eV) B _G膜(eV) 化合物實例2 -5.26 -4.23 1.03 化合物實例4 -5.28 -4.00 1.28 化合物實例4 A typical SWV experiment was run at 15 Hz frequency; 25 mV amplitude and 0.004 V increment step. Results were calculated for three freshly centrifuged membrane samples based on the HOMO and LUMO data. Table 2 HOMO film (eV) LUMO film (eV) B _G film (eV) Compound Example 2 -5.26 -4.23 1.03 Compound Example 4 -5.28 -4.00 1.28 Compound Example 4

如表2中所示，與化合物實例4相比，化合物實例2具有顯著更小的帶隙及顯著更深的LUMO。吸收率量測 As shown in Table 2, Compound Example 2 has a significantly smaller band gap and a significantly deeper LUMO than Compound Example 4. Absorbance Measurement

圖2顯示由15 mg/ml溶液壓延之膜及15 mg/ml溶液中之化合物實例2的吸收光譜。Figure 2 shows the absorption spectra of films cast from 15 mg/ml solutions and Compound Example 2 in 15 mg/ml solutions.

使用Cary 5000 UV-vis-IR光譜儀量測溶液及膜的吸收光譜。如圖2中所示，化合物實例2在膜中、在直至約1500 nm之波長下顯示吸收。裝置實例1 The absorption spectra of the solution and the film were measured using a Cary 5000 UV-vis-IR spectrometer. As shown in FIG2 , Compound Example 2 showed absorption in the film at wavelengths up to about 1500 nm. Device Example 1

製備具有以下結構之裝置：陰極/供體:受體層/陽極 Prepare a device with the following structure: Cathode/donor:acceptor layer/anode

用聚乙烯亞胺(PEIE)處理塗有氧化銦錫(ITO)層之玻璃基板以修改ITO之功函數。Glass substrates coated with indium tin oxide (ITO) were treated with polyethyleneimine (PEIE) to modify the work function of ITO.

供體聚合物1與化合物實例2 (受體)之混合物於1,2,4三甲苯:1,2-二甲氧基苯95:5 v/v溶劑混合物中的15 mg/ml溶液以1:1.5之供體:受體質量比、藉由棒塗沈積於改性之ITO層上。在80℃下、在真空下乾燥膜以形成約500 nm厚的本體異質接面層。A mixture of donor polymer 1 and compound Example 2 (acceptor) was deposited on the modified ITO layer by rod coating at a donor:acceptor mass ratio of 1:1.5 from a 15 mg/ml solution in a 1,2,4-trimethylbenzene:1,2-dimethoxybenzene 95:5 v/v solvent mixture. The film was dried at 80°C under vacuum to form a bulk heterojunction layer of about 500 nm thick.

在本體異質接面上藉由熱蒸發(MoO ₃)及濺鍍(ITO)形成MoO ₃(10 nm)及ITO (50 nm)之陽極堆疊。供體聚合物1 On the bulk heterojunction, an anode stack of MoO ₃ (10 nm) and ITO (50 nm) was formed by thermal evaporation (MoO ₃ ) and sputtering (ITO). Donor polymer 1

裝置實例7之EQE及暗電流分別顯示於圖3A及3B中。如圖3A中所示，波長在約1000至1300 nm之間時，達成超過10%的EQE。比較裝置1至3 The EQE and dark current of device example 7 are shown in Figures 3A and 3B, respectively. As shown in Figure 3A, an EQE of more than 10% is achieved at a wavelength between about 1000 and 1300 nm. Comparison devices 1 to 3

如關於裝置實例7所述製備比較裝置1至3，但其中改用比較供體聚合物1至3代替供體聚合物1：比較供體聚合物1 比較供體聚合物2 比較供體聚合物3 Comparative Devices 1 to 3 were prepared as described for Device Example 7, except that Comparative Donor Polymers 1 to 3 were used instead of Donor Polymer 1: Comparison with donor polymer 1 Comparison of donor polymer 2 Comparison of donor polymer 3

參看表3，儘管在HOMO偏移及帶隙方面類似，但含有供體聚合物1之裝置在1100 nm、1300 nm及1400 nm的外部量子效率顯著高於含有比較供體聚合物1、2或3之比較裝置的外部量子效率。例外之處為比較裝置1在1400 nm之EQE，然而此裝置受困於比裝置實例7高得多的暗電流。表3 裝置供體材料 HOMO 偏移 (eV) Eg (eV) Jd (mA/cm ²) EQE (%) 1100 nm 1300 nm 1400 nm 比較裝置1 比較供體聚合物1 0.21 0.82 0.79 11.56 6.69 2.31 比較裝置2 比較供體聚合物2 0.19 0.84 3.49 3.06 2.10 1.01 比較裝置3 比較供體聚合物3 0.42 0.61 0.11 0.36 0.58 0.51 裝置實例1 供體聚合物1 0.2 0.83 0.03 20.42 11.23 1.86 裝置實例2 Referring to Table 3, despite being similar in HOMO shift and bandgap, the external quantum efficiency of the device containing donor polymer 1 at 1100 nm, 1300 nm, and 1400 nm is significantly higher than that of the comparative devices containing comparative donor polymers 1, 2, or 3. The exception is the EQE of comparative device 1 at 1400 nm, however this device suffers from a much higher dark current than device Example 7. Table 3 Device Donor material HOMO shift (eV) Eg (eV) Jd (mA/cm ² ) EQE (%) 1100 nm 1300 nm 1400 nm Comparison device 1 Comparison with donor polymer 1 0.21 0.82 0.79 11.56 6.69 2.31 Comparison device 2 Comparison of donor polymer 2 0.19 0.84 3.49 3.06 2.10 1.01 Comparison device 3 Comparison of donor polymer 3 0.42 0.61 0.11 0.36 0.58 0.51 Device Example 1 Donor polymer 1 0.2 0.83 0.03 20.42 11.23 1.86 Device Example 2

如關於裝置實例1所述製備裝置，但其中改用受體1代替化合物實例2；供體:受體比率為1:1；且沈積10 mg/ml溶液以形成本體異質接面層： The device was prepared as described for Device Example 1, except that Acceptor 1 was used instead of Compound Example 2; the donor:acceptor ratio was 1:1; and a 10 mg/ml solution was deposited to form the bulk heterojunction layer:

受體1之膜的吸收光譜顯示於圖4A中。The absorption spectrum of the film of receptor 1 is shown in Figure 4A.

裝置實例8之EQE及暗電流分別顯示於圖4B及4C中。The EQE and dark current of Device Example 8 are shown in FIGS. 4B and 4C , respectively.

儘管已就具體例示性實施例描述本發明，但應瞭解，本文所揭示之特徵的各種修改、變更及/或組合對於熟習此項技術者為顯而易見的且不脫離如以下申請專利範圍中所闡述之本發明的範圍。Although the invention has been described with respect to specific exemplary embodiments, it should be understood that various modifications, variations and/or combinations of the features disclosed herein will be apparent to those skilled in the art without departing from the scope of the invention as set forth in the following claims.

101:基板 103:陰極 105:本體異質接面層 107:陽極 101: Substrate 103: Cathode 105: Body heterojunction layer 107: Anode

所揭示之技術及附圖描述所揭示之技術的一些實施方案。圖1繪示根據本揭示案之一實施例的有機光偵測器；圖2顯示受電子化合物之溶液及膜吸收光譜，其具有超過1000 nm之膜峰值吸收波長；圖3A為有機光偵測器之外部量子效率(EQE)相對於波長的曲線圖，其中光反應層含有具有苯并[1,2-b:4,5-b']二噻吩重複單元的供體聚合物2及化合物實例2；圖3B為圖3A之有機光偵測器暗電流密度相對於電壓的曲線圖；圖4A為受體1之膜吸收光譜；圖4B為有機光偵測器之外部量子效率(EQE)相對於波長的曲線圖，其中光反應層含有供體聚合物2及受體1；且圖4C為圖4B之有機光偵測器之暗電流密度相對於電壓的曲線圖。附圖未按比例繪製且具有各種視點及視角。附圖為一些實施方案及實例。另外，出於論述所揭示技術之一些實施例的目的，一些組分及/或操作可分成不同區塊或組合為單一區塊。此外，雖然該技術適於各種修改及替代形式，但具體實施例已舉例顯示於附圖中且在下文詳細描述。然而，不希望將該技術限於所述之特定實施方案。相反，希望該技術涵蓋屬於如所附申請專利範圍所定義的技術範圍內之所有修改、等效物及替代方案。 The disclosed technology and accompanying drawings describe some implementation schemes of the disclosed technology. FIG1 shows an organic photodetector according to an embodiment of the present disclosure; FIG2 shows the solution and film absorption spectra of an electron acceptor compound having a film peak absorption wavelength of more than 1000 nm; FIG3A is a graph of the external quantum efficiency (EQE) of an organic photodetector relative to wavelength, wherein the photoreaction layer contains a donor polymer 2 having a benzo[1,2-b:4,5-b']dithiophene repeating unit and compound example 2; FIG3B is a graph of the dark current density of the organic photodetector of FIG3A relative to voltage; FIG4A is a film absorption spectrum of acceptor 1; FIG4B is a graph of the external quantum efficiency (EQE) of an organic photodetector relative to wavelength, wherein the photoreaction layer contains a donor polymer 2 and an acceptor 1; and FIG. 4C is a graph of dark current density versus voltage for the organic photodetector of FIG. 4B . The accompanying figures are not drawn to scale and have various viewpoints and angles. The accompanying figures are some embodiments and examples. In addition, for the purpose of discussing some embodiments of the disclosed technology, some components and/or operations may be divided into different blocks or combined into a single block. In addition, although the technology is suitable for various modifications and alternative forms, specific embodiments have been illustrated in the accompanying figures and described in detail below. However, it is not desired to limit the technology to the specific embodiments described. Instead, it is desired that the technology cover all modifications, equivalents and alternatives that fall within the scope of the technology as defined in the attached patent application scope.

Claims

一種組合物，其包含供電子聚合物及受電子材料，其中該供電子聚合物包含苯并[1,2-b:4,5-b']二噻吩重複單元且其中該受電子材料之膜具有大於1000 nm的峰值吸收波長。A composition comprising an electron donating polymer and an electron accepting material, wherein the electron donating polymer comprises benzo[1,2-b:4,5-b']dithiophene repeating units and wherein a film of the electron accepting material has a peak absorption wavelength greater than 1000 nm.

如請求項1之組合物，其中該受電子材料為非芙受體。The composition of claim 1, wherein the electron accepting material is a non-electron acceptor.

如請求項2之組合物，其中該電子受體為式(I)化合物： EAG - EDG - EAG (I) 其中各EAG為受電子基團；且EDG為式(II)或(III)之供電子基團： (II) (III) 其中：各X獨立地為O或S； Ar ³及Ar ⁴在每次出現時獨立地為單環或多環芳族或雜芳族基團； Ar ⁵選自由以下組成之群：未取代或經一或兩個取代基取代的噻吩、呋喃及苯； R ¹及R ²在每次出現時獨立地為取代基； R ⁴及R ⁵各自獨立地為H或取代基； R ³及R ⁶各自獨立地為與EAG結合的H、取代基或二價基團； Z ¹為直接鍵或Z ¹與取代基R ⁴一起形成Ar ¹，其中Ar ¹為單環或多環芳族或雜芳族基團； Z ²為直接鍵或Z ²與取代基R ⁵一起形成Ar ²，其中Ar ²為單環或多環芳族或雜芳族基團； p為1、2或3； q為1、2或3；且 ----為連至EAG之連接點。 The composition of claim 2, wherein the electron acceptor is a compound of formula (I): EAG - EDG - EAG (I) wherein each EAG is an electron accepting group; and EDG is an electron donating group of formula (II) or (III): (II) (III) wherein: each X is independently O or S; Ar ³ and Ar ⁴ are independently monocyclic or polycyclic aromatic or heteroaromatic groups at each occurrence; Ar ⁵ is selected from the group consisting of thiophene, furan and benzene which are unsubstituted or substituted with one or two substituents; R ¹ and R ² are independently substituents at each occurrence; R ⁴ and R ⁵ are independently H or a substituent; R ³ and R ⁶ are independently H, a substituent or a divalent group bound to EAG; Z ¹ is a direct bond or Z ¹ and substituent R ⁴ together form Ar ¹ , wherein Ar ¹ is a monocyclic or polycyclic aromatic or heteroaromatic group; Z ² is a direct bond or Z ² and substituent R ⁵ together form Ar ² , wherein Ar ² is a monocyclic or polycyclic aromatic or heteroaromatic group; p is 1, 2 or 3; q is 1, 2 or 3; and ---- is the connection point to EAG.

如請求項3之組合物，其中Ar ³及Ar ⁴各自獨立地選自噻吩、呋喃、呋喃并呋喃及噻吩并噻吩。 The composition of claim 3, wherein Ar ³ and Ar ⁴ are each independently selected from thiophene, furan, furanofuran and thienothiophene.

如請求項3或4之組合物，其中EAG選自式(IIa)及(IIIa)： (IIa) (IIIa)。 The composition of claim 3 or 4, wherein EAG is selected from formula (IIa) and (IIIa): (IIa) (IIIa).

如請求項3或4之組合物，其中EAG選自式(IIb)及(IIIb)： (IIb) (IIIb) 其中R ⁷在每次出現時獨立地為H或取代基。 The composition of claim 3 or 4, wherein EAG is selected from formula (IIb) and (IIIb): (IIb) (IIIb) wherein R ⁷ at each occurrence is independently H or a substituent.

如請求項3之組合物，其中p及q中之至少一者為2。The composition of claim 3, wherein at least one of p and q is 2.

如請求項3之組合物，其中Z ¹連接至R ⁴以形成單環芳族或雜芳族基團且/或Z ²連接至R ⁵以形成單環芳族或雜芳族基團。 The composition of claim 3, wherein Z ¹ is linked to R ⁴ to form a monocyclic aromatic or heteroaromatic group and/or Z ² is linked to R ⁵ to form a monocyclic aromatic or heteroaromatic group.

如請求項8之組合物，其中Z ¹連接至R ⁴以形成噻吩環或噻吩并噻吩且/或Z ²連接至R ⁵以形成噻吩環或噻吩并噻吩。 The composition of claim 8, wherein Z ¹ is connected to R ⁴ to form a thiophene ring or thienothiophene and/or Z ² is connected to R ⁵ to form a thiophene ring or thienothiophene.

如請求項3之組合物，其中各EAG為式(V)之基團： (V) 其中： R ¹⁰在每次出現時為H或取代基； ----表示連至EDG的連接位置；且各X ¹至X ⁴獨立地為CR ¹³或N，其中R ¹³在每次出現時為H或取代基。 The composition of claim 3, wherein each EAG is a group of formula (V): (V) wherein: R ¹⁰ is H or a substituent at each occurrence; ---- represents the attachment position to EDG; and each X ¹ to X ⁴ is independently CR ¹³ or N, wherein R ¹³ is H or a substituent at each occurrence.

如請求項10之組合物，其中各R ¹³獨立地選自H；C _1-12烷基；及吸電子基團。 The composition of claim 10, wherein each R ¹³ is independently selected from H; C _1-12 alkyl; and an electron withdrawing group.

如請求項11之組合物，其中該吸電子基團為F或CN。The composition of claim 11, wherein the electron-withdrawing group is F or CN.

如請求項3之組合物，其中R ¹及R ²在每次出現時選自由以下組成之群：直鏈、分支鏈或環狀C _1-20烷基，其中一個或多個不相鄰的非末端C原子可經O、S、NR ¹²、CO或COO置換，其中R ¹²為C _1-12烴基且該C _1-20烷基中的一個或多個H原子可經F置換；且式(Ak)u-(Ar ⁶)v之基團，其中Ak為C _1-12伸烷基鏈，其中一個或多個C原子可經O、S、CO或COO置換；u為0或1；Ar ⁶在每次出現時獨立地為未取代或經一個或多個取代基取代的芳族或雜芳族基團；且v至少為1。 A composition as claimed in claim 3, wherein R ¹ and R ² are selected from the group consisting of: a linear, branched or cyclic C _1-20 alkyl group, wherein one or more non-adjacent non-terminal C atoms can be replaced by O, S, NR ¹² , CO or COO, wherein R ¹² is a C _1-12 alkyl group and one or more H atoms in the C _1-20 alkyl group can be replaced by F; and a group of formula (Ak)u-(Ar ⁶ )v, wherein Ak is a C _1-12 alkyl chain, wherein one or more C atoms can be replaced by O, S, CO or COO; u is 0 or 1; Ar ⁶ is independently, at each occurrence, an aromatic or heteroaromatic group which is unsubstituted or substituted by one or more substituents; and v is at least 1.

如請求項3之組合物，其中各R ³至R ⁶獨立地選自： H； C _1-12烷基，其中一個或多個不相鄰的非末端C原子可經O、S、COO或CO置換；且芳族或雜芳族基團Ar ⁵，其未取代或經一個或多個取代基取代。 The composition of claim 3, wherein each R ³ to R ⁶ is independently selected from: H; C _1-12 alkyl, wherein one or more non-adjacent non-terminal C atoms may be replaced by O, S, COO or CO; and an aromatic or heteroaromatic group Ar ⁵ which is unsubstituted or substituted by one or more substituents.

如請求項6之組合物，其中各R ⁷在每次出現時獨立地選自： H； C _1-12烷基，其中一個或多個不相鄰的非末端C原子可經O、S、COO或CO置換；且芳族或雜芳族基團Ar ⁵，其未取代或經一個或多個取代基取代。 The composition of claim 6, wherein each R ⁷ is independently selected at each occurrence from: H; C _1-12 alkyl, wherein one or more non-adjacent non-terminal C atoms may be replaced by O, S, COO or CO; and an aromatic or heteroaromatic group Ar ⁵ which is unsubstituted or substituted by one or more substituents.

如請求項1之組合物，其中該苯并[1,2-b:4,5-b']二噻吩重複單元為式(X)之重複單元： (X) 其中R ¹⁷及R ¹⁸各自獨立地選自H；F；C _1-12烷基，其中一個或多個不相鄰的非末端C原子可經O、S、COO或CO置換且該烷基中的一個或多個H原子可經F置換；或芳族基團Ar ²，其未取代或經一個或多個選自F及C _1-12烷基的取代基取代，其中一個或多個不相鄰的非末端C原子可經O、S、COO或CO置換。 The composition of claim 1, wherein the benzo[1,2-b:4,5-b']dithiophene repeating unit is a repeating unit of formula (X): (X) wherein R ¹⁷ and R ¹⁸ are each independently selected from H; F; a C _1-12 alkyl group, wherein one or more non-adjacent non-terminal C atoms may be replaced by O, S, COO or CO and one or more H atoms in the alkyl group may be replaced by F; or an aromatic group Ar ² which is unsubstituted or substituted with one or more substituents selected from F and a C _1-12 alkyl group, wherein one or more non-adjacent non-terminal C atoms may be replaced by O, S, COO or CO.

一種調配物，其包含溶解於或分散於一種或多種溶劑中的如請求項1之組合物。A formulation comprising the composition of claim 1 dissolved or dispersed in one or more solvents.

一種有機光偵測器，其包含：陽極；陰極；以及安置於該陽極與該陰極之間的光敏有機層，其中該光敏有機層包含如請求項1之組合物。An organic photodetector comprises: an anode; a cathode; and a photosensitive organic layer disposed between the anode and the cathode, wherein the photosensitive organic layer comprises the composition of claim 1.

一種形成如請求項18之有機光偵測器的方法，其包含在該陽極及該陰極中之一者上形成該光敏有機層以及在該光敏有機層上形成該陽極及該陰極中之另一者，其中形成該光敏有機層包含沈積調配物，該調配物包含溶解於或分散於一種或多種溶劑中的電子受體及供電子聚合物。A method of forming an organic photodetector as claimed in claim 18, comprising forming the photosensitive organic layer on one of the anode and the cathode and forming the other of the anode and the cathode on the photosensitive organic layer, wherein forming the photosensitive organic layer comprises depositing a formulation comprising an electron acceptor and an electron donating polymer dissolved or dispersed in one or more solvents.

一種光感測器，其包含光源及如請求項18之有機光偵測器，該有機光偵測器經組態以偵測自該光源發射的光，其中該光源發射具有大於1000 nm之峰值波長的光。A photo sensor comprising a light source and an organic photodetector as claimed in claim 18, wherein the organic photodetector is configured to detect light emitted from the light source, wherein the light source emits light having a peak wavelength greater than 1000 nm.