Membranes, electrets, vibration-generating elements, organic light-emitting elements, molecular design methods and programs

Abstract

To derive a general formula of a compound exhibiting a giant surface potential when formed into a membrane, and realize a membrane with a large surface potential useful as an electret material.SOLUTION: The membrane contains a compound represented by the general formula (1) in the figure. In the general formula (1), R represents a fluoroalkyl group; and none to two of the X, Y and Z represent fluoroalkyl groups while the remainder represents substituents other than fluoroalkyl groups.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a film useful as an electret material, a compound useful as a material for the film, an electret, a vibration power generation element, and an organic light-emitting element using the film, as well as a molecular design method for the compound and a program for carrying out the molecular design method. [Background technology]

[0002] Electrostatic vibration power generation elements are known as vibration power generation elements that convert vibrations into electricity. Electrostatic vibration power generation elements are power generation elements that are configured to use vibrations to change the relative position of an electret (electric stone) and an electrode, thereby sequentially inducing electrostatic induction in the electrodes. Because of their advantage of being able to efficiently extract electricity from low-frequency vibrations with small accelerations, such as environmental vibrations, research and development into these elements is actively underway. For example, research and development of electrets, a vibration-powered energy harvesting element, has traditionally focused on polymer-based electrets, in which an electric charge is implanted into a polymer film. However, implanting an electric charge into a polymer film (poling) is a process carried out using methods such as corona discharge and electron beam irradiation, which requires large-scale equipment such as a high-voltage power supply and is a complicated process, resulting in low productivity and high costs. Recently, a vibration power generation element has been reported that utilizes the surface potential that spontaneously occurs in an organic thin film during the film formation process. For example, Patent Document 1 describes the use of a laminate in which polar molecules are layered on an electrode as the electret of the vibration power generation element. Examples of polar molecules mentioned here include Al(7-Prq)3, Oxd-7, Alq3, TPBi, and BCP. These polar molecules can be layered on the electrode by film formation methods such as vapor deposition and coating, which is said to improve the manufacturing efficiency and reduce the cost of vibration power generation elements compared to those that use charge implantation processes. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2020-36423 Summary of the Invention [Problem to be solved by the invention]

[0004] As described above, Patent Document 1 describes the use of an organic thin film formed from polar molecules as an electret. However, when the present inventors evaluated the giant surface potential (GSP) of the polar molecule film described in Patent Document 1, they found that it was not fully satisfactory. Furthermore, Patent Document 1 only describes specific examples of polar molecules that can be used in electrets, but does not provide molecular design guidelines such as the molecular structure required to achieve a large surface potential, the range of that molecular structure, or the molecular structure that determines the positive or negative polarity of the surface potential. Therefore, even if you look at the description in Patent Document 1, it is difficult to improve the polar molecules described therein to realize an electret that exhibits a desired surface potential.

[0005] In order to solve the problems of the conventional technology, the present inventors have conducted extensive research to derive a general formula for a compound that exhibits a large surface potential when formed into a film. Furthermore, they have continued their research with the aim of realizing a film that exhibits a large surface potential and is useful as an electret material. [Means for solving the problem]

[0006] As a result of intensive research to solve the above problems, the present inventors have found that a film exhibiting a giant positive or negative surface potential can be obtained by forming a film from a compound having a structure in which substituents are bonded to four bonds of a carbon atom, where one to three of the substituents are fluoroalkyl groups and the remaining are substituents other than fluoroalkyl groups. They also found that a vibration power generation element using this film as an electret film exhibits good power generation characteristics. The present invention has been proposed based on these findings and specifically has the following configuration.

[0007] [1] A film containing a compound represented by the following general formula (1): [ka] (In general formula (1), R represents a fluorinated alkyl group, 0 to 2 of X, Y, and Z each independently represent a fluorinated alkyl group, and the remaining each independently represent a substituent other than a fluorinated alkyl group.) [2] The film according to [1], wherein X is a fluoroalkyl group, and Y and Z are each independently a substituent other than a fluoroalkyl group. [3] The membrane according to [2], wherein Y and Z are each independently a donor group. [4] The film according to [2], wherein Y and Z are each independently an acceptor group. [5] The film according to any one of [2] to [4], wherein Y and Z are each independently a substituted aryl group. [6] The film according to any one of [2] to [5], wherein Y and Z have the same structure. [7] The film according to [1], wherein X, Y and Z are substituents other than fluorinated alkyl groups. [8] The membrane according to [7], wherein X, Y and Z have the same structure. [9] The membrane according to [7] or [8], wherein X, Y, and Z are each independently a substituted aryl group.

[10] The film according to [5] or [9], wherein the substituted aryl group is a heteroaryl group containing a nitrogen atom in the ring skeleton, a diarylamino group (two aryl groups constituting the diarylamino group may be bonded to each other via a single bond or a linking group), or an aryl group substituted with a group containing a cyano group.

[11] The membrane according to any one of [1] to

[10] , wherein when one or two of X, Y, and Z represent a fluorinated alkyl group, the fluorinated alkyl group and the fluorinated alkyl group of R have the same structure.

[12] An electret having the film according to any one of [1] to

[11] .

[13] A vibration power generating element having the film according to any one of [1] to

[11] .

[14] An organic light-emitting device having the film according to any one of [1] to

[11] .

[15] The organic light-emitting device according to

[14] , wherein the compound is represented by the following general formula (1-1): [ka] (In the general formula (1-1), R 1 represents a fluorinated alkyl group, and X 1 ,Y 1 and Z 1 0 to 2 of X each independently represent a fluorinated alkyl group, and the remaining X each independently represent a substituent other than a fluorinated alkyl group. 1 ,Y 1 and Z 1 X of 1 When only Y is a fluorinated alkyl group, 1 and Z 1 are each independently a donor group, or are each independently an acceptor group other than a fluorinated alkyl group.

[16] A compound represented by the following general formula (1-1): [ka] (In the general formula (1-1), R 1 represents a fluorinated alkyl group, and X 1 ,Y 1 and Z 1 0 to 2 of X each independently represent a fluorinated alkyl group, and the remaining X each independently represent a substituent other than a fluorinated alkyl group. 1 When Y is a fluorinated alkyl group, 1 and Z 1 are each independently a donor group, or are each independently an acceptor group other than a fluorinated alkyl group.

[17] A molecular design method comprising a step of selecting a specific compound from the compounds represented by the general formula (1) and a substituted compound obtained by substituting at least one selected from R, X, Y, and Z of the specific compound, which has a high evaluation based on an index including a permanent dipole moment.

[18] The molecular design method according to

[17] , wherein the evaluation indexes include the magnitude and direction of the permanent dipole moment and the rigidity of the molecule.

[19] The molecular design method according to

[18] , wherein the rigidity of the molecule is evaluated by glass transition temperature.

[20] The molecular design method according to any one of

[17] to

[19] , further comprising evaluating the molecular orientation state during film formation.

[21] The molecular design method according to any one of

[17] to

[20] , which comprises determining whether a GSP is positive or negative.

[22] A program for carrying out the molecular design method according to any one of

[17] to

[21] . [Effects of the Invention]

[0008] When a film is formed from the compound represented by general formula (1) used in the present invention, a large positive or negative surface potential is generated. The film of the present invention exhibits a large surface potential by containing such a compound, making it useful as an electret film. A vibration power generation element using the film of the present invention can achieve excellent power generation characteristics synchronized with the vibration of a vibration mechanism. [Brief explanation of the drawings]

[0009] [Figure 1] 1 is a schematic longitudinal sectional view showing a first embodiment of a vibration-based power generator to which the present invention is applied. [Figure 2] FIG. 10 is a schematic vertical cross-sectional view showing a second embodiment of a vibration-based power generator to which the present invention is applied. [Figure 3] FIG. 10 is a schematic vertical cross-sectional view showing a third embodiment of a vibration-based power generator to which the present invention is applied. [Figure 4] 1 is a graph showing the film thickness dependency of the surface potential of each film of Compounds 1 to 5. [Figure 5] 1 is a graph showing the film thickness dependency of the surface potential of the film of Compound 6. [Figure 6] 1 is a graph showing the film thickness dependency of the surface potential of the film of Compound 7. [Figure 7]1 is a graph showing the current density-voltage characteristics of HOD element 1 using compound 1 in the buffer layer, HOD element 2 using compound 2 in the buffer layer, HOD element 3 using compound 6 in the buffer layer, comparative HOD element 1 having no buffer layer, and comparative HOD element 2 using TPBi in the buffer layer. [Figure 8] 1 is a graph showing the current density-voltage characteristics of EOD element 1, which uses compound 1 for the buffer layer; EOD element 2, which uses compound 6 for the buffer layer; EOD element 3, which uses a layered structure of compound 1 / compound 6 for the buffer layer; EOD element 4, which uses a layered structure of compound 6 / compound 1 for the buffer layer; and comparative EOD element 1, which does not have a buffer layer. [Figure 9] FIG. 1 is a schematic vertical cross-sectional view showing the vibration power generating elements produced in Examples 13 and 14. [Figure 10] FIG. 10 is a plan view of an electret included in the vibration power generation element of FIG. [Figure 11] 1 is a graph showing the time change in generated current of a vibration power generating element 1 using a film of Compound 1 as an electret. [Figure 12] 10 is a graph showing the time change in generated current of a vibration power generating element 2 using a film of Compound 6 as an electret. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present invention will be described in detail below. The following description of the constituent elements may be based on representative embodiments or specific examples, but the present invention is not limited to such embodiments. In this specification, a numerical range expressed using "to" means a range including the numerical values ​​before and after "to" as the lower and upper limits. In addition, the isotopes of hydrogen atoms present in the molecules of the compounds used in the present invention are not particularly limited, and for example, when all hydrogen atoms in the molecule are 1 H, or part or all of 2 It may also be H (deuterium D).

[0011] <Membrane> The film of the present invention is characterized by containing a compound represented by the following general formula (1). The compound represented by the following general formula (1) has a fluorinated alkyl group and a non-fluorinated alkyl group bonded to one carbon atom (central atom), resulting in a polarized state in which the charge is biased to one side within the molecule. Therefore, when this compound is formed into a film, giant positive or negative surface electrons are generated. The film of the present invention, containing such a compound represented by general formula (1), exhibits a large positive or negative surface potential. The polarity and magnitude of the film's surface potential can be controlled by selecting the structure (direction and magnitude of the dipole) and combination of the substituents (R, X, Y, and Z) of the compound represented by general formula (1), the film thickness, etc. The structure of the compound represented by general formula (1) contained in the film of the present invention will be explained below.

[0012] [Compound represented by general formula (1)] [ka]

[0013] In general formula (1), R represents a fluorinated alkyl group, 0 to 2 of X, Y and Z each independently represent a fluorinated alkyl group, and the remaining each independently represent a substituent other than a fluorinated alkyl group. In the present invention, the term "fluorinated alkyl group" refers to a group having a structure in which at least one hydrogen atom of an alkyl group is substituted with a fluorine atom. The fluorinated alkyl group may be a perfluoroalkyl group in which all hydrogen atoms of the alkyl group are substituted with fluorine atoms, or a partially fluorinated alkyl group in which only some of the hydrogen atoms of the alkyl group are substituted with fluorine atoms. Of these, the fluorinated alkyl group is preferably a perfluoroalkyl group. The number of carbon atoms of the fluorinated alkyl group is preferably 1 to 20, more preferably 1 to 10, even more preferably 1 to 5, and particularly preferably 1 to 3. When the number of carbon atoms of the fluorinated alkyl group is 3 or more, the fluorinated alkyl group may be linear or branched. When one or two of X, Y, and Z represent a fluorinated alkyl group, the fluorinated alkyl group and the fluorinated alkyl group of R may have the same structure or different structures, but preferably have the same structure. Examples of when the fluorinated alkyl group represented by R and the fluorinated alkyl group represented by one or two of X, Y, and Z are different from each other include when the number of carbon atoms or the number of fluorine atoms is different, when the fluorinated alkyl group is linear or branched, or when the number or position of branches in a branched fluorinated alkyl group is different. The combination of the substituents X, Y, and Z may be such that X is a fluorinated alkyl group and Y and Z are each independently a substituent other than a fluorinated alkyl group, or X and Y are each independently a fluorinated alkyl group and Z is a substituent other than a fluorinated alkyl group, or X, Y, and Z are each independently a substituent other than a fluorinated alkyl group. Among these, preferred is when X is a fluorinated alkyl group and Y and Z are each a substituent other than a fluorinated alkyl group, or when X, Y, and Z are all substituents other than a fluorinated alkyl group. When X is a fluorinated alkyl group and Y and Z are all substituents other than a fluorinated alkyl group, the substituents Y and Z may have the same structure or different structures, but preferably have the same structure. When X, Y, and Z are all substituents other than a fluorinated alkyl group, the substituents X, Y, and Z may have the same structure or different structures, but preferably have the same structure.

[0014] Substituents other than fluorinated alkyl groups that X, Y, and Z can have include donor groups and acceptor groups other than fluorinated alkyl groups. Here, the term "donor group" as used herein refers to a group that is a group having a Hammett σ p The term "acceptor group" as used herein refers to a substituent having a Hammett σ p represents a substituent whose value is positive. "Hammett's σ pThe "value" was proposed by L.P. Hammett and quantifies the effect of a substituent on the reaction rate or equilibrium of a para-substituted benzene derivative. Specifically, the following equation holds between the substituent in a para-substituted benzene derivative and the reaction rate constant or equilibrium constant: log(k / k0) = ρσ p or log(K / K0) = ρσ p The constants specific to the substituents in p ) In the above formula, k is the rate constant of the benzene derivative without a substituent, k0 is the rate constant of the benzene derivative substituted with a substituent, K is the equilibrium constant of the benzene derivative without a substituent, K0 is the equilibrium constant of the benzene derivative substituted with a substituent, and ρ is a reaction constant determined by the type and conditions of the reaction. p The explanation of "value" and the numerical values ​​of each substituent are given in Hansch, C. et al., Chem. Rev., 91, 165-195 (1991). p See the description of Hammett's σ p Substituents with negative values ​​exhibit electron donating (donor) properties, and Hammett's σ p Substituents with positive values ​​tend to exhibit electron-withdrawing (accepting) properties. In the following explanation, "Hammett's σ p "Hammett's σ value is negative" is called "electron donating" p A positive value is sometimes called "electron-withdrawing." Preferably, two or three of X, Y, and Z are donor groups or acceptor groups other than fluorinated alkyl groups, and more preferably two. That is, more preferably, X is a fluorinated alkyl group, and Y and Z are each independently a donor group or an acceptor group other than fluorinated alkyl groups. Here, the combination of Y and Z may be any combination in which both Y and Z are donor groups, both Y and Z are acceptor groups other than fluorinated alkyl groups, or one of Y and Z is a donor group and the other is an acceptor group other than fluorinated alkyl groups. However, it is preferred that Y and Z are each independently a donor group or that Y and Z are each independently an acceptor group other than fluorinated alkyl groups, and more preferably, Y and Z are donor groups having the same structure or that Y and Z are acceptor groups having the same structure.

[0015] Substituents other than the fluorinated alkyl group that X, Y, and Z may have include substituted aryl groups. The substituted aryl group may be a donor group or an acceptor group, and may be a group having a Hammett σ p It may also be a group with a value of 0. The aromatic ring constituting the aryl group in the substituted aryl group may be a single ring, a fused ring in which two or more aromatic rings are fused, or a linked ring in which two or more aromatic rings are linked. When two or more aromatic rings are linked, they may be linked in a linear or branched chain. The number of carbon atoms in the aromatic ring constituting the aryl group is preferably 6 to 40, more preferably 6 to 22, even more preferably 6 to 18, even more preferably 6 to 14, and particularly preferably 6 to 10. Specific examples of the aryl group include a phenyl group, a naphthalenyl group, and a biphenyl group.

[0016] Preferred examples of the substituted aryl group include a heteroaryl group containing a nitrogen atom in the ring skeleton, a diarylamino group (two aryl groups constituting the diarylamino group may be bonded to each other via a single bond or a linking group), and an aryl group substituted with a group containing a cyano group.

[0017] The heterocycle (nitrogen-containing aromatic heterocycle) constituting the heteroaryl group containing a nitrogen atom in the ring skeleton may be a monocycle or a fused ring in which one or more heterocycles are fused with one or more aromatic rings or heterocycles. The number of carbon atoms in the nitrogen-containing aromatic heterocycle constituting the heteroaryl group is preferably 3 to 40, more preferably 5 to 22, even more preferably 5 to 18, still more preferably 5 to 14, and particularly preferably 5 to 10. Specific examples of the nitrogen-containing aromatic heterocycle include a pyridine ring, a pyridazine ring, a pyrimidine ring, a triazole ring, a fused ring in which two or more of these nitrogen-containing six-membered rings are fused, and a fused ring in which these nitrogen-containing six-membered rings are fused with an aromatic hydrocarbon ring such as a benzene ring.

[0018] For the explanation, preferred ranges and specific examples of the aryl group constituting the diarylamino group, please refer to the explanation, preferred ranges and specific examples of the aryl group in the "substituted aryl group" above. The diarylamino group is preferably a diphenylamino group. The two aryl groups constituting the diarylamino group may be bonded to each other via a single bond or a linking group. A specific example of two aryl groups constituting the diarylamino group bonded to each other via a single bond is a carbazol-9-yl group. The linking group connecting the two aryl groups constituting the diarylamino group is preferably a linking group with a linking chain length of one atom. Specific examples of linking groups include -O-, -S-, -N(R 91 )- or -C(R 92 )(R 93 )-, where R 91 ~R 93 R each independently represents a hydrogen atom or a substituent. 91 Examples of the substituent that R may have include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, and a heteroaryl group having 3 to 40 carbon atoms. 92 and R 93Examples of the substituents that may be taken by each independently include a hydroxy group, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an alkyl-substituted amino group having 1 to 20 carbon atoms, an aryl-substituted amino group having 1 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, a heteroaryl group having 3 to 40 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkylamido group having 2 to 20 carbon atoms, an arylamido group having 7 to 21 carbon atoms, and a trialkylsilyl group having 3 to 20 carbon atoms. Specific examples of diarylamino groups in which two aryl groups are bonded via a linking group include a 10H-phenoxazin-10-yl group, a 10H-phenothiazin-10-yl group, a 9,10-dihydro-9,9-dialkylacridin-10-yl group, and a 5,10-dihydro-10-phenylphenazin-5-yl group.

[0019] The group containing a cyano group may be a cyano group or an organic group substituted with a cyano group. An example of an organic group substituted with a cyano group is an aryl group. For the description, preferred range, and specific examples of the aryl group, please refer to the description, preferred range, and specific examples of the aryl group in the above "substituted aryl group." The number of cyano groups substituted in the organic group is not particularly limited, and may be one or two or more.

[0020] The substituent in the substituted aryl group may be further substituted with a substituent, examples of which include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, and a heteroaryl group having 3 to 40 carbon atoms.

[0021] It is preferred that two or three of X, Y, and Z are substituted aryl groups. Specifically, it is preferred that X is a fluorinated alkyl group, and Y and Z are each independently a substituted aryl group, or that X, Y, and Z are each independently a substituted aryl group. When Y and Z are substituted aryl groups, these substituted aryl groups may have the same structure or different structures, but it is preferred that they have the same structure. Furthermore, when X, Y, and Z are substituted aryl groups, these substituted aryl groups may have the same structure or different structures, but it is preferred that they have the same structure.

[0022] Substituents other than fluorinated alkyl groups that X, Y and Z may have include aryl groups substituted with hydrocarbon ring groups. For the explanation, preferred range and specific examples of the aryl group, please refer to the explanation, preferred range and specific examples of the aryl group in the "substituted aryl group" above. The hydrocarbon ring group is a monovalent group obtained by removing one hydrogen atom from a cyclic hydrocarbon. The cyclic hydrocarbon may be an alicyclic hydrocarbon or an aromatic hydrocarbon, and may have a polycyclic condensed structure. Examples of the hydrocarbon ring group include a monovalent group obtained by removing one hydrogen atom from a polycyclic aromatic hydrocarbon such as a pyrene ring or an anthracene ring, a fullerenyl group (C 60 ), adamantyl group, etc.

[0023] Preferred examples of the substituents other than fluorinated alkyl groups that X, Y and Z may have are given below: In the following formulae, * represents the bonding position to the carbon atom in general formula (1). First, examples of substituents that generally contribute to the induction of a negative potential are listed below. However, even if a compound has these substituents, the surface potential of the film may become positive depending on the structure of other substituents in the compound.

[0024] [ka] JPEG0007793139000006.jpg221170

[0025] The following are examples of substituents that generally contribute to the induction of a positive potential. However, even if a compound has these substituents, the surface potential of the film may become negative depending on the structure of other substituents in the compound.

[0026] [ka] JPEG0007793139000008.jpg162170

[0027] The compound represented by general formula (1) is preferably a compound represented by the following general formula (1-1).

[0028] [ka]

[0029] In general formula (1-1), R 1 represents a fluorinated alkyl group, and X 1 ,Y 1 and Z 1 0 to 2 of X each independently represent a fluorinated alkyl group, and the remaining X each independently represent a substituent other than a fluorinated alkyl group. 1 ,Y 1 and Z 1 X of 1 When only Y is a fluorinated alkyl group, 1 and Z 1 are each independently a donor group, or are each independently an acceptor group other than a fluorinated alkyl group. For the explanation and preferred range of the "fluorinated alkyl group", please refer to the explanation and preferred range of the "fluorinated alkyl group" of the general formula (1) above. X 1 , Y 1 and Z 1 When one or two of the groups represent fluorinated alkyl groups, the fluorinated alkyl groups and R 1 The fluorinated alkyl groups may have the same structure or different structures, but preferably have the same structure. X 1 , Y 1 and Z 1 The combination of substituents is X 1 is a fluorinated alkyl group, and Y 1 and Z 1 may each independently be a substituent other than a fluorinated alkyl group, and X 1 and Y 1 is a fluorinated alkyl group, and Z 1 may be a substituent other than a fluorinated alkyl group, and X 1 , Y 1 and Z 1 may each independently be a substituent other than a fluorinated alkyl group. 1 , Y 1 and Z 1 Of these, X 1 When only Y is a fluorinated alkyl group, 1 and Z 1 are each independently a donor group, or are each independently an acceptor group other than a fluorinated alkyl group. For an explanation of the "donor group" and the "acceptor group", please refer to the explanation of the "donor group" and the "acceptor group" given as examples of the "substituent other than a fluorinated alkyl group" in the explanation of the general formula (1) above. Among these, X 1 is a fluorinated alkyl group, and Y 1 and Z 1 are each independently a donor group, X 1 is a fluorinated alkyl group, and Y 1 and Z 1 are each independently an acceptor group, X 1 , Y 1 and Z 1 are each independently a substituent other than a fluorinated alkyl group. 1 is a fluorinated alkyl group, and Y 1 and Z 1 is a donor group, Y 1 and Z 1 The donor groups X may have the same structure or different structures, but are preferably donor groups having the same structure. 1 is a fluorinated alkyl group, and Y1 and Z 1 When Y is an acceptor group other than a fluorinated alkyl group, 1 and Z 1 The acceptor groups X may have the same structure or different structures, but are preferably acceptor groups of the same structure. 1 , Y 1 and Z 1 When all of are substituents other than fluorinated alkyl groups, X 1 , Y 1 and Z 1 The substituents may have the same structure or different structures, but preferably have the same structure. For preferred ranges and specific examples of the "substituent other than a fluorinated alkyl group," reference can be made to the description of the "substituent other than a fluorinated alkyl group" in general formula (1). In addition, among the examples of the "substituent other than a fluorinated alkyl group," those that are donor groups can also be referred to as examples of donor groups, and among the examples of the "substituent other than a fluorinated alkyl group," those that are acceptor groups can also be referred to as examples of acceptor groups.

[0030] Preferred specific examples of the compound represented by general formula (1) are given below. Among compounds 1, 1a, and 2 to 12, compounds 1, 1a, 2 to 5, and 8 to 11 are compounds that contribute to the induction of a negative surface potential, and compounds 6, 7, and 12 are compounds that contribute to the induction of a positive surface potential.

[0031] [ka] JPEG0007793139000011.jpg103170

[0032] Furthermore, specific examples of the compound represented by general formula (1) include compounds represented by the following general formula (1-2): 2 , Y 2 , Z 2are the substituents shown in Tables 1 and 2. Sn1 to Sn30 and Sp1 to Sp25 in Tables 1 and 2 are the numbers of the substituents given above as examples of substituents other than fluorinated alkyl groups. Of the compounds shown below, compounds 13 to 51 are compounds that contribute to the induction of a negative surface potential, and compounds 52 to 92 are compounds that contribute to the induction of a positive surface potential. However, the compounds represented by general formula (1) that can be used in the present invention should not be construed as being limited by these specific examples.

[0033] [ka]

[0034] [Table 1]

[0035] [Table 2]

[0036] Among the compounds that contribute to the induction of a negative surface potential, more preferred are compounds 1, 13 to 31, and particularly preferred are compounds 1, 13 to 21. Furthermore, among the compounds that contribute to the induction of a positive surface potential, more preferred are compounds 6, 7, and 52 to 72, and particularly preferred are compounds 7, and 52 to 61.

[0037] [Film composition] The film of the present invention may contain one or more compounds represented by general formula (1). The film of the present invention may contain only the compound represented by general formula (1), or may contain the compound represented by general formula (1) and components other than the compound represented by general formula (1) (other components). Examples of other components include a host material. The host material is a matrix material that maintains the molecules of the compound represented by general formula (1) in a certain orientation. It is preferably an organic material that is solid at room temperature and has a permanent dipole moment of 1 Debye or less. By selecting the host material and adjusting the compounding ratio between the host material and the compound represented by general formula (1), the orientation state of the molecules of the compound represented by general formula (1) can be controlled, thereby controlling the surface potential of the film. Specific examples of host materials include CBP, used in the examples, as well as SF3-TRZ and TCTA. When the film contains a host material, the content of the compound represented by general formula (1) in the film is preferably 10 to 99% by weight, more preferably 50 to 99% by weight, and even more preferably 70 to 95% by weight.

[0038] [Method of film formation] The method for forming the film of the present invention is not particularly limited, and may be either a dry process or a wet process, but it is preferable to use a dry process, and it is more preferable to use a vacuum deposition method.

[0039] [Film Thickness] The thickness of the film of the present invention is preferably 100 nm or more, and may be 500 nm or more, or 1000 nm or more, from the viewpoint of developing a sufficient surface potential. The upper limit of the film thickness is not particularly limited, and may be 10000 nm or less, 1000 nm or less, or 500 nm or less.

[0040] [Giant membrane surface potential] The membrane of the present invention exhibits a positive or negative surface potential on its surface due to the structure and polarization of the compound represented by general formula (1). The membrane of the present invention preferably exhibits a film thickness dependency (giant surface potential), in which the surface potential changes depending on the thickness of the membrane. Here, the degree of the giant surface potential can be measured by the slope of the approximation line in a plot where the surface potential of the membrane is plotted on the vertical axis and the film thickness on the horizontal axis. In the following description, this slope is referred to as the "giant surface potential slope," and the sign of the slope (+ or -) is referred to as the "polarity of the giant surface potential." The polarity of the giant surface potential may be positive or negative. When the membrane exhibits a positive giant surface potential, the slope of the giant surface potential is preferably 50 mV / nm or more, more preferably 80 mV / nm or more, and even more preferably 100 mV / nm or more. When the membrane exhibits a negative giant surface potential, the slope of the giant surface potential is preferably -50 mV / nm or less, more preferably -80 mV / nm or less, and even more preferably -100 mV / nm or less.

[0041] <Electret> The electret of the present invention is characterized by having the film of the present invention. For a description of the membrane of the present invention, please refer to the description in the <Membrane> section above. As described above, the film of the present invention exhibits a surface potential on its surface, and therefore can be effectively used as an electret material. Furthermore, the polarity and magnitude of the surface potential exhibited by the film of the present invention can be controlled over a wide range by selecting the structure (direction and magnitude of the dipole) and combination of the substituents (R, X, Y, and Z) of the compound represented by general formula (1), the film thickness, the compound type of the host material, and the compounding ratio between the host material and the compound represented by general formula (1). Therefore, the electret of the present invention can be applied to various elements that use electrets. The film of the present invention used for the electret may exhibit a positive surface potential or a negative surface potential. The electret has, for example, a substrate and an electret film provided on the substrate, and the electret film is composed of the film of the present invention. The electret may also have components other than the substrate and the electret film. For example, an electrode made of a conductive material may be provided between the substrate and the electret film. The surface potential of the electret film varies depending on the application of the electret, but when it is a positive surface potential, it is preferably 100 V or more, may be 500 V or more, or may be 1000 V or more. The upper limit of the positive surface potential is not particularly limited, but is usually 10,000 V or less. When it is a negative surface potential, it is preferably -100 V or less, may be -500 V or less, or may be -1000 V or less. The lower limit of the negative surface potential is not particularly limited, but is usually -10,000 V or more.

[0042] <Vibration power generation element> The vibration power generating element of the present invention is characterized by having the film of the present invention. For an explanation of the film of the present invention, please refer to the description in the above section on <Film>. The film of the present invention used in the vibration power generation element may be a film that exhibits a positive surface potential, a film that exhibits a negative surface potential, or both a film that exhibits a positive surface potential and a film that exhibits a negative surface potential. Examples of the vibration power generation element of the present invention include a vibration power generator and a vibration sensor. The vibration power generator is configured to vibrate at least one of the membrane and the counter electrode of the present invention to induce charge in the counter electrode and extract the charge as a current. The vibration sensor is configured to detect the vibration of the vibration detection object by vibrating at least one of the membrane and the counter electrode in conjunction with the vibration when the vibration detection object vibrates, and to use the current due to the charge induced in the counter electrode by the vibration as a detection signal. Structural examples of vibration-driven power generators are shown in Figures 1 to 3. In the following description, the vibration-driven power generator shown in Figure 1 will be referred to as the first embodiment, the vibration-driven power generator shown in Figure 2 will be referred to as the second embodiment, and the vibration-driven power generator shown in Figure 3 will be referred to as the third embodiment. The vibration power generator (first embodiment) shown in FIG. 1 has an electret 1, an electrode substrate 2 arranged opposite to the electret 1, and a load resistor 3. The electret 1 has an electret substrate 10, an electrode 11 provided on the surface of the electret substrate 10 facing the electrode substrate 2, and an electret film 12 provided on the surface of the electrode 11 opposite the electret substrate 10, and the electrode 11 is electrically connected to a load resistor 3. In this vibration power generator, the electret film 12 is made of the film of the present invention. The electrode substrate 2 has a substrate 20 and a counter electrode 21 provided on the surface of the substrate 20 facing the electret 1, and the counter electrode 21 is electrically connected to a load resistor 3. The electrode substrate 2 is supported so that the surface of the counter electrode 21 faces the surface of the electret film 12 at a distance from it, and is configured to vibrate in the normal direction to the surface of the electret film 12 by a vibration mechanism. In this vibration power generator, when the electrode substrate 2 vibrates due to the operation of the vibration mechanism, the counter electrode 21 moves back and forth between a position close to the surface of the electret film 12 (close position) and a position away from it (remote position). Here, for example, if the surface potential of the electret film 12 is positive, at the close position, a positive electrostatic field formed near the surface of the electret film 12 induces a negative charge on the surface of the counter electrode 21, and the opposite charge (positive charge) flows toward the load resistor, generating a first current. Also, when the second electrode 21 moves from the close position to the remote position, the negative charge bound by the electrostatic field is released and flows toward the load resistor, generating a second current opposite to the first current. Also, if the surface potential of the electret film 12 is negative, at the close position, a positive charge is induced on the surface of the counter electrode 21, and the opposite charge (negative charge) flows toward the load resistor, generating a first current. Furthermore, when the second electrode 21 moves from the close position to the separate position, the positive charge bound by the electrostatic field is released and flows toward the load resistor, generating a second current in the opposite direction to the first current. Through the above operations, this vibration-driven power generator generates a current in a pattern corresponding to the polarity of the surface potential of the electret film. The vibration-driven power generator (second embodiment) shown in Fig. 2 is configured similarly to the vibration-driven power generator of the first embodiment, except that a spacer 13 is provided to surround the periphery of the electret film 12. The spacer 13 is made of an insulating material such as resin, and has an upper surface that is higher than the surface of the electret film 12. This spacer 13 functions to keep the distance between the surface of the electret film 12 and the surface of the counter electrode 21 constant when the counter electrode 21 moves to the close position. The vibration power generator (third embodiment) shown in FIG. 3 is configured in the same manner as the vibration power generator of the first embodiment, except that a second electret 2a is used instead of the electrode substrate 2. That is, the vibration power generator of the third embodiment is configured to include a first electret 1a, a second electret 2a disposed opposite to the first electret 1a, and a load resistor 3. The first electret 1a has a first electret substrate 10a, a first electrode 11a provided on the surface of the first electret substrate 10a facing the second electret 2a, and a first electret film 12a provided on the surface of the first electrode 11a opposite to the first electret substrate 10a, and the first electrode 11a is electrically connected to the load resistor 3. In the first electret 1a, the first electret film 12a is made of the film of the present invention having a positive surface potential. The second electret 2a has a second electret substrate 20a, a second electrode 21a provided on the surface of the second electret substrate 20a on the first electret side 1a, and a second electret film 22a provided on the surface of the second electrode 21a opposite the second electret substrate 20a, and the second electrode 21a is electrically connected to a load resistor 3. In the second electret 2a, the second electret film 22a is composed of the film of the present invention having a negative surface potential. The second electret 2a is supported so that the surface of the second electret film 22a faces the surface of the first electret film 12a at a distance, and is configured to vibrate in the normal direction to the surface of the first electret film 12a by a vibration mechanism. In the vibration-induced power generator of the third embodiment, when the second electret 2a vibrates due to the operation of the vibration mechanism, the second electret film 12a moves back and forth between a position close to the surface of the first electret film 12a (close position) and a position away from the surface of the first electret film 12a (separate position). At the close position, a positive electrostatic field formed near the surface of the first electret film 12a induces a negative charge on the surface of the second electrode 21a, and a negative electrostatic field formed near the surface of the second electret film 22a induces a positive charge on the surface of the first electrode 11a. Then, in each electrode 11a, charges opposite in direction to the induced charges flow toward the load resistor, generating a first current. Furthermore, when the second electret film 22a moves from the close position to the separated position, the negative charge on the second electrode 21a and the positive charge on the first electrode 11a, which had been bound by the electrostatic field, are released and flow toward the load resistor 3, generating a second current opposite in direction to the first current. This vibration power generator generates power by inducing charges in both the first electrode 11a and the second electrode 21a through the above operation, and therefore can obtain larger power. In the vibration power generator of the third embodiment, instead of the second electret 2a vibrating, the first electret 1a may be configured to vibrate, or both the first electret 1a and the second electret 2a may be configured to vibrate. Alternatively, the first electret film 12a and the second electret film 22a may be arranged side by side, and the second electrode 21a and the first electrode 11a may be arranged side by side so as to face each other, with the second electrode 21a vibrating in the normal direction to the surface of the first electret film 12a and the first electrode 11a vibrating in the normal direction to the surface of the second electret film 22a. In this case, too, electric charges are induced in both the first electrode 11a and the second electrode 21a, generating electricity, and thus larger electric power can be obtained.

[0043] <Organic light-emitting element> The organic light-emitting device of the present invention is characterized by having the film of the present invention. For an explanation of the film of the present invention, please refer to the description in the above section of <Film>. The film of the present invention used in the organic light-emitting device may be a film that exhibits a positive surface potential, a film that exhibits a negative surface potential, or both a film that exhibits a positive surface potential and a film that exhibits a negative surface potential. The film used in the organic light-emitting device preferably contains a compound represented by general formula (1-1). For an explanation of the compound represented by general formula (1-1), please refer to the description of general formula (1-1) in the <Film> section above. The organic light-emitting device of the present invention may be an organic photoluminescence device (organic PL device) or an organic electroluminescence device (organic EL device), but is preferably an organic electroluminescence device. The organic photoluminescence device has a structure in which at least an emitting layer and the film of the present invention are formed on a substrate. The organic electroluminescence device has a structure in which at least an anode, a cathode, and an organic layer are formed between the anode and the cathode. The organic layer includes at least an emitting layer and the film of the present invention. It may consist of only the emitting layer and the film of the present invention, or it may also have one or more additional organic layers. Examples of such other organic layers include a hole transport layer, a hole injection layer, an electron blocking layer, a hole blocking layer, an electron injection layer, an electron transport layer, and an exciton blocking layer. The hole transport layer may be a hole injection transport layer having a hole injection function, and the electron transport layer may be an electron injection transport layer having an electron injection function. Materials for these organic layers can be selected from known materials. The film of the present invention may be disposed in any position in an organic light-emitting device. In the case of an organic electroluminescence device, however, it is preferable to dispose the film of the present invention having a negative surface potential between the anode and the light-emitting layer. It is more preferable to dispose this film in contact with the anode or between the hole injection layer and the light-emitting layer so as to be in contact with the hole injection layer. This can promote hole injection from the anode to the organic layer. Alternatively, a laminate structure of the film of the present invention having a negative surface potential and the film of the present invention having a positive surface potential can be disposed between the light-emitting layer and the cathode so that the film having the positive surface potential is on the cathode side. It is preferable to dispose this laminate structure so that the film having the positive surface potential is in contact with the cathode or between the electron injection layer and the light-emitting layer so that it is in contact with the electron injection layer. This can promote electron injection from the cathode to the organic layer.

[0044] <Compound> The compound of the present invention is a compound having a structure represented by the above general formula (1-1). For an explanation of the compound represented by the general formula (1-1), please refer to the description of the general formula (1-1) in the above <Membrane> section. The compound represented by general formula (1-1) is a novel compound and can be synthesized by the Sandmeyer bromination of starting materials such as 2,2-bis(4-aminophenyl)hexafluoropropane, followed by the Suzuki-Miyaura coupling reaction.

[0045] <Molecular design method> The molecular design method of the present invention is a molecular design method comprising a step of selecting a specific compound from among compounds represented by general formula (1) and a substituted compound obtained by substituting at least one selected from R, X, Y, and Z of the specific compound, which has a high evaluation based on an index including a permanent dipole moment. For an explanation of the compound represented by general formula (1) and the preferred ranges and specific examples of R, X, Y, and Z, please refer to the corresponding descriptions in the <Film> section above. In the present invention, "evaluation based on an index" means, for example, calculating the index values ​​of a specific compound and a substituted compound, and evaluating highly a compound that exhibits an index value closer to a target index value. In the molecular design method of the present invention, evaluation is performed based on indices including the permanent dipole moment, and by repeating the above steps, compounds that exhibit the target polarization state or a polarization state close to the target polarization state can be selected from the compounds represented by general formula (1). By forming a film of such compounds, a film with the desired surface potential can be obtained. The evaluation indices used in the present invention preferably include the magnitude and direction of the permanent dipole moment and the rigidity of the molecule, which allows precise design of molecules that induce a desired surface potential. Here, the magnitude and direction of the permanent dipole moment can be calculated. For a specific method for calculating the permanent dipole moment, see the description in the Examples section. The molecular rigidity is preferably evaluated by the glass transition temperature. The glass transition temperature is the temperature at which the physical properties of the object to be measured, such as viscosity and fluidity, change drastically when the temperature is continuously changed. The higher the glass transition temperature, the higher the molecular rigidity can be evaluated. The glass transition temperatures of the specific compound and the substituted compound can be calculated based on the measured glass transition temperatures of their respective analogous compounds. In the evaluation performed in the present invention, it is preferable to further evaluate the molecular orientation state during film formation. By adding this evaluation, it is possible to more precisely design a compound that induces a desired surface potential. The molecular orientation state during film formation can be predicted from the film formation conditions. Film formation conditions that can be used to predict the orientation state include the film formation method (evaporation method or coating method), the composition of the coating material used in the coating method (whether it is a single solution of the compound represented by general formula (1) or a mixed solution that also contains a host material), and the compound type of the host material used in combination. Furthermore, in the molecular design method of the present invention, it is preferable to clarify the positive and negative of the GSP (giant surface potential). The positive and negative of the GSP can be determined by calculation. For specific calculation methods, please refer to the description in the Examples section.

[0046] <Program> The program of the present invention is a program for carrying out the molecular design method of the present invention. For the steps of the program of the present invention, the description of the steps in the molecular design method of the present invention can be referred to. The data stored in the database of the compound represented by general formula (1) can use the physical property values ​​exemplified as evaluation indexes in the molecular design method of the present invention. [Example]

[0047] The features of the present invention are further illustrated by the following examples and comparative examples. The materials, amounts, ratios, treatment details, and treatment procedures shown in the following examples can be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below. The surface potential of the film was measured in a dark place under vacuum using an ultra-high vacuum Kelvin probe system (KP Technology: UHVKP020) by the Kelvin probe method, with the ITO (indium tin oxide) potential as the origin. The permanent dipole moment of the molecule and the polarity of the giant surface potential were calculated using Gaussian DFT at the B3LYP 6-31G(d) calculation level.

[0048] Compounds used in this example The compounds used in this example are the following compounds 1, 1a, and 2 to 12.

[0049] [ka] JPEG0007793139000016.jpg105169

[0050] [1] Preparation and evaluation of a single film of the compound represented by general formula (1) Example 1 Preparation of a film of Compound 1 Several glass substrates were prepared with indium tin oxide (ITO) films of 100 nm thickness. Each ITO film was vacuum-deposited under a vacuum of 5 × 10 ―4 Compound 1 was evaporated to a thickness of 100 nm or less under conditions of 0.1 Pa or less, and various films with different thicknesses were prepared. The evaporation rate of Compound 1 was 1.0 angstrom / second.

[0051] Examples 2 to 5: Preparation of films of compounds 2 to 5 Various films with different thicknesses were prepared in the same manner as in Example 1, except that the compounds shown in Table 1 were used instead of Compound 1.

[0052] Example 6 Preparation of a film of Compound 6 Films with different thicknesses were prepared in the same manner as in Example 1, except that Compound 6 was used instead of Compound 1 and the deposition rate of Compound 6 was changed within the range of 0.5 to 3.0 angstroms / second.

[0053] Example 7 Preparation of a film of Compound 7 Various films with different thicknesses were prepared in the same manner as in Example 1, except that Compound 7 was used instead of Compound 1.

[0054] The surface potential of the films prepared in Examples 1 to 5 was measured, and the results of examining the film thickness dependence of the surface potential are shown in Figure 4. The surface potential of the film prepared in Example 6 was measured, and the results of examining the film thickness dependence of the surface potential are shown in Figure 5. The surface potential of the film prepared in Example 7 was measured, and the results of examining the film thickness dependence of the surface potential are shown in Figure 6. Table 3 also shows the calculated values ​​of the permanent dipole moment (PDM) of the compounds used in each Example and the giant surface potential slope (GSP slope) calculated from the approximation lines in Figures 4 to 7. Table 3 also shows the types of substituents X, Y, and Z for each compound.

[0055] [Table 3]

[0056] As shown in Table 3, by changing the substituents X, Y, and Z of the compounds, the permanent dipole moment (PDM) of the compound molecule and the slope of the giant surface potential (GSP) of the membrane changed. For example, the slope of the giant surface potential of the membrane of compounds 1 to 5 is negative, while the slope of the giant surface potential of the membrane of compounds 6 and 7 is positive. This is because the CF3 side of compounds 1 to 5 is δ - (negative charge), and in compounds 6 and 7, the CF3 side is δ + The polarity (sign of the gradient) and magnitude (absolute value of the gradient) of the giant surface potential of such a membrane can be controlled by the direction and magnitude of the dipoles of the substituents X, Y, and Z.

[0057] Example 8: Computational evaluation of films of compounds 1a, 8 to 12 The calculated permanent dipole moments (PDM) and giant surface potential slopes (GSP slopes) for compounds 1a and 8 to 12 are shown in Table 4. Compound 1a is compound 1 with a different number of carbon atoms in the fluorinated alkyl group.

[0058] [Table 4]

[0059] [2] Preparation and evaluation of a mixed film of the compound represented by general formula (1) and a host material Example 9 Preparation of a mixed membrane of Compound 1 and CBP Several glass substrates with 100 nm thick indium tin oxide (ITO) films were prepared. On each ITO, vacuum deposition was performed at a vacuum level of 5 x 10 ―4 Compound 1 and CBP were co-deposited from different deposition sources under the condition of Pa to prepare various co-deposited films (mixed films) with different thicknesses. The concentration of Compound 1 in the mixed films was set to 15 wt% or 50 wt%.

[0060] Examples 10 and 11: Preparation of mixed membranes of compound 2 and CBP, and mixed membranes of compound 6 and CBP Films with different thicknesses and compound concentrations were prepared in the same manner as in Example 1, except that compound 2 or compound 6 was used instead of compound 1 to form a co-deposited film.

[0061] The giant surface potential slope (GSP slope) measured for the mixed films prepared in Examples 9 to 11 is shown in Table 5. Table 5 also shows the measurement results for the single films prepared in Examples 1, 2, and 6 above.

[0062] [Table 5]

[0063] As shown in Table 5, the slope of the giant surface potential (GSP slope) changed by changing the concentrations of compounds 1, 2, and 6. This indicates that the giant surface potential of the film can be controlled by forming a film from the compound represented by general formula (1) and a host material and changing the compound concentration.

[0064] [3] Fabrication and evaluation of hole transport devices using films of compounds represented by general formula (1) Here, a film of the compound represented by general formula (1) was formed between the anode and the organic layer. Hereinafter, this film containing the compound represented by general formula (1) will be referred to as the "first buffer layer."

[0065] Experimental Example 1: Fabrication of a hole transport element using Compound 1 in the first buffer layer Each thin film was deposited by vacuum deposition on a glass substrate with an anode made of indium tin oxide (ITO) with a thickness of 100 nm, at a vacuum level of 1×10 ―5 The layers were laminated at a pressure of 0.1 Pa or less. First, Compound 1 was deposited on ITO to a thickness of 2 nm to form a film (first buffer layer). Next, NPD was evaporated to a thickness of 100 nm to form a hole transport layer, and aluminum (Al) was evaporated to a thickness of 100 nm to form an electrode on top of that, producing a hole transport device (HOD device 1). Experimental Examples 2 and 3: Fabrication of a hole transport device using Compound 2 or Compound 6 in the first buffer layer Various hole transport devices (HOD devices 2 and 3) were fabricated in the same manner as in Experimental Example 1, except that the first buffer layer was formed using Compound 2 or Compound 6 instead of Compound 1.

[0066] Comparative Experimental Example 1: Fabrication of a hole transport element without a first buffer layer A hole transport element (Comparative HOD element 1) was fabricated in the same manner as in Experimental Example 1, except that the first buffer layer was not formed.

[0067] Comparative Experimental Example 2: Fabrication of a hole transport element using TPBi as a buffer layer A hole transport device (comparative HOD device 2) was fabricated in the same manner as in Experimental Example 1, except that TPBi was used instead of Compound 1 to form the buffer layer.

[0068] FIG. 7 shows the measurement results of the current density-voltage characteristics of the hole transport devices fabricated in each experimental example and each comparative experimental example. As shown in Figure 7, HOD devices 1 and 2, in which the first buffer layer was formed using Compound 1 or Compound 2, which exhibit a giant negative surface potential, showed increased current density in a lower voltage range than the comparative HOD device 1, which did not have a buffer layer. This indicates that, among the compounds represented by general formula (1), compounds that exhibit a giant negative surface potential exhibit the effect of promoting hole injection.

[0069] [4] Fabrication and evaluation of electron transport devices using compounds represented by general formula (1) Here, a film (single layer film) of the compound represented by general formula (1) or a laminated film of two such films was formed between the organic layer and the cathode. Hereinafter, this single layer film will be referred to as the "second buffer layer," and the layer of the laminated film on the electron transport layer side will be referred to as the "second buffer layer," and the layer on the electron injection layer side will be referred to as the "third buffer layer."

[0070] Experimental Example 4: Fabrication of an electron transport device using Compound 1 in the second buffer layer Each thin film was deposited by vacuum deposition on a glass substrate with an electrode made of indium tin oxide (ITO) with a thickness of 100 nm, at a vacuum of 1×10 ―5 The layers were stacked at a pressure of 0.1 Pa or less. First, Liq was deposited on the ITO to a thickness of 2 nm, and T2T was evaporated on top of that to a thickness of 100 nm to form an electron transport layer. Next, Compound 1 was evaporated to a thickness of 5 nm to form a second buffer layer. Subsequently, Liq was evaporated to a thickness of 2 nm to form an electron injection layer, and aluminum (Al) was evaporated on top of that to a thickness of 100 nm to form a cathode, resulting in an electron transport device (EOD device 1).

[0071] Experimental Example 5: Fabrication of an electron transport device using Compound 6 in the second buffer layer An electron transporting device (EOD device 2) was fabricated in the same manner as in Experimental Example 4, except that Compound 6 was used instead of Compound 1 to form the second buffer layer.

[0072] (Experimental Example 6) Fabrication of an electron transport device using a buffer layer with a two-layer structure (compound 1 / compound 6) A Liq layer and a hole transport layer were formed in this order on ITO in the same manner as in Experimental Example 2. Next, Compound 1 was evaporated to a thickness of 4 nm to form a second buffer layer, and Compound 6 was evaporated to a thickness of 1 nm to form a third buffer layer thereon. Subsequently, Liq was evaporated to a thickness of 2 nm to form an electron injection layer, and aluminum (Al) was evaporated to a thickness of 100 nm to form a cathode thereon, to produce an electron transport device (EOD device 3).

[0073] Experimental Example 7: Preparation of an electron transport layer using a buffer layer with a two-layer structure (compound 6 / compound 1) A Liq layer and a hole transport layer were formed in this order on ITO in the same manner as in Experimental Example 2. Next, Compound 6 was evaporated to a thickness of 4 nm to form a second buffer layer, and Compound 1 was evaporated to a thickness of 1 nm to form a third buffer layer thereon. Subsequently, Liq was evaporated to a thickness of 2 nm to form an electron injection layer, and aluminum (Al) was evaporated to a thickness of 100 nm to form a cathode thereon, to produce an electron transport device (EOD device 4).

[0074] Comparative Experimental Example 3: Fabrication of an electron transport element without a buffer layer An electron transporting device (Comparative EOD Device 1) was fabricated in the same manner as in Experimental Example 4, except that the buffer layer was not formed.

[0075] FIG. 8 shows the measurement results of the current density-voltage characteristics of the electron transport devices fabricated in each experimental example and each comparative experimental example. As shown in Figure 8, EOD device 1, which had a two-layer buffer layer (compound 1 / compound 6) in which compound 1, which exhibits a huge negative surface potential, was on the electron transport layer side and compound 6, which exhibits a huge positive surface potential, was on the cathode side, had a higher current density in a low voltage region than comparative EOD device 1, which did not have a buffer layer. This indicates that electron injection is promoted by adopting a layered structure of electron transport layer / compound exhibiting a huge negative surface potential (second buffer layer) / compound exhibiting a huge positive surface potential (third buffer layer) / electron injection layer / cathode.

[0076] [5] Fabrication of organic light-emitting devices using films of compounds represented by general formula (1) Example 12: Preparation of an organic light-emitting device using Compound 1 in the first and second buffer layers and Compound 6 in the third buffer layer Each thin film was deposited by vacuum deposition on a glass substrate with an anode made of indium tin oxide (ITO) with a thickness of 100 nm, at a vacuum level of 1×10 ―5 The layers were laminated at a pressure of 0.1 Pa or less. First, a 5 nm thick film (first buffer layer) of compound 2 was deposited on ITO. Next, a 30 nm thick NPD film was deposited as a hole transport layer, and a 30 nm thick layer was formed as an emissive layer by co-evaporating CBP and 4CzIPN from different evaporation sources. The concentration of 4CzIPN was 15 wt%. Next, a 100 nm thick film of T2T was deposited as an electron transport layer. Next, a 4 nm thick second buffer layer was formed by evaporation of compound 1, and a 1 nm thick third buffer layer was formed on top of that by evaporation of compound 6. Next, a 2 nm thick electron injection layer was formed by evaporation of Liq, and a 100 nm thick cathode was formed on top of that, completing the organic electroluminescence device.

[0077] [6] Evaluation of vibration-powered energy harvesting devices using films of compounds represented by general formula (1) The structure of the vibration power generation element produced in this example is shown in FIG. 9, and the structure of the electret of this vibration power generation element is shown in FIG. The vibration power generating element shown in FIG. 9 includes an electret 100 and an electrode substrate 200 that vibrates in the normal direction to the film surface of the electret 100. 10, the electret 100 has an ITO-attached substrate 101, an electret film 103 provided on the ITO 102, and a spacer 104 surrounding the electret film 103. The electret film 103 is composed of a vapor-deposited film of a compound represented by general formula (1). The electrode substrate 200 has a substrate 201 that is vibrated by a vibration mechanism, and an ITO electrode (counter electrode) 202 provided on the electret side 100 of the substrate 201, and is arranged so that the surface of the counter electrode 202 faces the surface of the electret film 103. In this vibration power generation element, the counter electrode 202 is connected to an oscilloscope 301 via an amplifier 300, and the time change in the current generated in the counter electrode 202 can be observed on the oscilloscope 301. In the vibration power generation element configured as described above, when the counter electrode 202 approaches the electret film 103 due to vibration of the electrode substrate 200, an electrostatic field formed near the surface of the electret film 103 induces charges in the counter electrode 202, generating a first current. Furthermore, when the counter electrode 202 moves away from the electret film 103, the charges bound by the electrostatic field are released, generating a second current opposite to the first current. Specifically, when the surface potential of the electret film 103 is negative, a negative first current is generated when the counter electrode 202 approaches the electret film 103, and a positive second current is generated when the counter electrode 202 moves away from the electret film 103. On the other hand, when the surface potential of the electret film 103 is positive, a positive first current is generated when the counter electrode 202 approaches the electret film 103, and a negative second current is generated when the counter electrode 202 moves away from the electret film 103.

[0078] Example 13: Evaluation of a vibration power generation element using Compound 1 as an electret film The vibration power generation element shown in Figure 9 was fabricated using the following process. A glass substrate with a 100 nm thick indium tin oxide (ITO) film was prepared. A thin film was deposited on the ITO film by vacuum deposition at a vacuum level of 1×10 ―4 An electret film was formed by depositing Compound 1 to a thickness of 3.3 μm under conditions of 0.1 Pa or less. Subsequently, a spacer was formed around this electret film using SU-8 (manufactured by Gersteltec) to form an electret. This electret was incorporated into the vibration power generation element shown in Figure 9, and the electrode substrate was vibrated to measure the time change in the generated current. The results are shown in Figure 11. As shown in Figure 11, the generation of current synchronized with the vibration was observed from this vibration power generation element.

[0079] Example 14: Evaluation of a vibration power generation element using Compound 6 as an electret film An electret was prepared in the same manner as in Example 13, except that Compound 6 was used instead of Compound 1 to form the electret. This electret was incorporated into the vibration power generation element shown in Figure 9, and the electrode substrate was vibrated to measure the time change in the generated current. The results are shown in Figure 12. As shown in Figure 12, the generation of current synchronized with the vibration was observed from this vibration power generation element.

[0080] [ka] [Industrial Applicability]

[0081] The film of the present invention exhibits a surface potential induced by the compound represented by general formula (1), and the surface potential can be controlled to a desired value by selecting a compound within the range of general formula (1). Therefore, the film of the present invention is useful as an electret material, and by using this to construct a vibration power generation element, good power generation characteristics can be obtained. Therefore, the present invention has high industrial applicability. [Explanation of symbols]

[0082] 1 electret 10 Electret substrate 11 electrodes 12 Electret film 13 Spacer 2. Electrode substrate 20 PCB 21 Counter electrode 3 Load Resistance 1a First electret 10a First electret substrate 11a 1st electrode 12a First electret film 2a Second electret 20a Second electret substrate 21a 2nd electrode 22a Second electret film

Claims

1. A film containing a compound represented by the following general formula (1): 【Chemistry 1】 In general formula (1), R represents a fluorinated alkyl group, 0 to 2 of X, Y, and Z each independently represent a fluorinated alkyl group, and the remaining each independently represent a substituent other than a fluorinated alkyl group. However, general formula (1) satisfies at least one of the following conditions (A) to (D): (A) X, Y and Z are substituents other than fluorinated alkyl groups and have the same structure. (B) X, Y and Z are each independently a substituted aryl group. (C) The substituent other than the fluorinated alkyl group represented by the remainder of X, Y, and Z is an aryl group substituted with a hydrocarbon ring group consisting of an alicyclic hydrocarbon or a polycyclic aromatic hydrocarbon, or a substituent selected from the following substituent group a: (Substituent group a) 【Chemistry 2】 * indicates the bonding position to the carbon atom in general formula (1). (D) The substituents other than the fluorinated alkyl group represented by the remainder of X, Y, and Z are all aryl groups substituted with diarylamino groups substituted with heteroaryl groups having 3 to 40 carbon atoms (the two aryl groups constituting the diarylamino group may be bonded to each other via a single bond or a linking group), or are all substituents selected from the following substituent group b: (Substituent group b) 【Transformation 3】 * indicates the bonding position to the carbon atom in general formula (1).

2. 2. The membrane of claim 1, wherein X is a fluorinated alkyl group, and Y and Z are each independently a substituent other than a fluorinated alkyl group.

3. 3. The membrane of claim 2, wherein Y and Z are each independently a donor group.

4. 3. The membrane of claim 2, wherein Y and Z are each independently an acceptor group.

5. The membrane of any one of claims 2 to 4, wherein Y and Z have the same structure.

6. 2. The membrane of claim 1, wherein X, Y, and Z in (A) are substituted aryl groups.

7. 2. The membrane according to claim 1, wherein the substituted aryl group in (B) is a heteroaryl group containing a nitrogen atom in its ring skeleton, a diarylamino group (two aryl groups constituting the diarylamino group may be bonded to each other via a single bond or a linking group), or an aryl group substituted with a group containing a cyano group.

8. The membrane according to any one of claims 1 to 7, wherein when one or two of X, Y, and Z represent a fluorinated alkyl group, the fluorinated alkyl group and the fluorinated alkyl group of R have the same structure.

9. An electret comprising the film according to any one of claims 1 to 8.

10. A vibration power generating element having the film according to any one of claims 1 to 8.

11. An organic light-emitting device comprising the film according to any one of claims 1 to 8.

12. The organic light-emitting device according to claim 11, wherein the compound is represented by the following general formula (1-1): 【Chemistry 4】 (In general formula (1-1), R １ represents a fluorinated alkyl group, and X １ , Y １ and Z １ 0 to 2 of X independently represent a fluorinated alkyl group, and the remaining X independently represent a substituent other than a fluorinated alkyl group. １ , Y １ and Z １ X of １ When only Y is a fluorinated alkyl group, １ and Z １ are each independently a donor group, or are each independently an acceptor group other than a fluorinated alkyl group, provided that general formula (1-1) satisfies at least one of the following conditions (A) to (D): (A) X, Y and Z are substituents other than fluorinated alkyl groups and have the same structure. (B) X, Y and Z are each independently a substituted aryl group. (C) The substituent other than the fluorinated alkyl group represented by the remainder of X, Y, and Z is an aryl group substituted with a hydrocarbon ring group consisting of an alicyclic hydrocarbon or a polycyclic aromatic hydrocarbon, or a substituent selected from the following substituent group a: (Substituent group a) 【Transformation 5】 * indicates the bonding position to the carbon atom in general formula (1-1). (D) The substituents other than the fluorinated alkyl group represented by the remainder of X, Y, and Z are all aryl groups substituted with diarylamino groups substituted with heteroaryl groups having 3 to 40 carbon atoms (the two aryl groups constituting the diarylamino group may be bonded to each other via a single bond or a linking group), or are all substituents selected from the following substituent group b: (Substituent group b) 【Transformation 6】 * indicates the bonding position to the carbon atom in general formula (1-1).

13. A compound represented by the following general formula (1-1): 【Transformation 7】 (In general formula (1-1), R １ represents a fluorinated alkyl group, and X １ , Y １ and Z １ 0 to 2 of X independently represent a fluorinated alkyl group, and the remaining X independently represent a substituent other than a fluorinated alkyl group. １ is a fluorinated alkyl group, Y １ and Z １ are each independently a donor group, or are each independently an acceptor group other than a fluorinated alkyl group, provided that general formula (1-1) satisfies at least one of the following conditions (A) to (D): (A) X, Y and Z are substituents other than fluorinated alkyl groups and have the same structure. (B) X, Y and Z are each independently a substituted aryl group. (C) The substituent other than the fluorinated alkyl group represented by the remainder of X, Y, and Z is an aryl group substituted with a hydrocarbon ring group consisting of an alicyclic hydrocarbon or a polycyclic aromatic hydrocarbon, or a substituent selected from the following substituent group a: (Substituent group a) 【Transformation 8】 * indicates the bonding position to the carbon atom in general formula (1-1). (D) The substituents other than the fluorinated alkyl group represented by the remainder of X, Y, and Z are all aryl groups substituted with diarylamino groups substituted with heteroaryl groups having 3 to 40 carbon atoms (the two aryl groups constituting the diarylamino group may be bonded to each other via a single bond or a linking group), or are all substituents selected from the following substituent group b: (Substituent group b) 【Chemistry 9】 * indicates the bonding position to the carbon atom in general formula (1-1).

14. An electret film having a negative polarity of the giant surface potential, comprising a compound represented by the following general formula (1): 【Chemistry 10】 (In general formula (1), R represents a fluorinated alkyl group, 0 to 2 of X, Y, and Z each independently represent a fluorinated alkyl group, and the remaining each independently represent a substituent selected from the following substituent group c.) (Substituent group c) 【Chemistry 11】 【change】 * indicates the bonding position to the carbon atom in general formula (1).

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