(19)
(11)EP 3 524 610 A1

(12)EUROPEAN PATENT APPLICATION

(43)Date of publication:
14.08.2019 Bulletin 2019/33

(21)Application number: 19164312.1

(22)Date of filing:  05.08.2010
(51)Int. Cl.: 
C07D 495/04  (2006.01)
C07D 495/22  (2006.01)
C07D 495/14  (2006.01)
H01L 51/00  (2006.01)
(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

(30)Priority: 05.08.2009 GB 0913628

(62)Application number of the earlier application in accordance with Art. 76 EPC:
18198795.9 / 3447057
16002060.8 / 3141551
10852323.4 / 2462146

(71)Applicant: Cambridge Display Technology Limited
Cardinal Way Godmanchester Cambridgeshire PE29 2XG (GB)

(72)Inventors:
  • ZUBERI, Sheena
    Godmanchester, PE29 2XG (GB)
  • ZUBERI, Tania
    Godmanchester, PE29 2XG (GB)

(74)Representative: Grünecker Patent- und Rechtsanwälte PartG mbB 
Leopoldstraße 4
80802 München
80802 München (DE)

 
Remarks:
This application was filed on 21-03-2019 as a divisional application to the application mentioned under INID code 62.
 


(54)ORGANIC SEMICONDUCTORS


(57) A compound comprising a structure of formula (II):

where R1 to R4 independently are selected from optionally substituted straight, branched or cyclic alkyl chains having between 2 and 20 carbon atoms, alkoxy, amino, amido, silyl, alkenyl, aryl and hetero aryl; where X1 and X2 independently represent S or O; where Ar1 and Ar2 are heterocyclic aromatic rings respectively comprising one heteroatom selected from S and O, and where n is an integer between 1 and 4; and wherein one or both of the terminal aromatic groups of the compound is substituted with one or more polymerisable groups T, and wherein each T is independently selected from halogen, boronic acid, diboronic acid, boronic ester, diboronic acid ester, alkylene and stannyl.


Description


[0001] The present invention relates generally to organic semiconductors and in particular to organic semiconductors for forming part of a thin film transistor.

[0002] Transistors can be divided into two main types: bipolar junction transistors and field-effect transistors. Both types share a common structure comprising three electrodes with a semiconductive material disposed there between in a channel region. The three electrodes of a bipolar junction transistor are known as the emitter, collector and base, whereas in a field-effect transistor the three electrodes are known as the source, drain and gate. Bipolar junction transistors may be described as current-operated devices as the current between the emitter and collector is controlled by the current flowing between the base and emitter. In contrast, field-effect transistors may be described as voltage-operated devices as the current flowing between source and drain is controlled by the voltage between the gate and the source.

[0003] Transistors can also be classified as p-type and n-type according to whether they comprise semiconductive material which conducts positive charge carriers (holes) or negative charge carriers (electrons) respectively. The semiconductive material may be selected according to its ability to accept, conduct, and donate charge. The ability of the semiconductive material to accept, conduct and donate holes or electrons can be enhanced by doping the material.

[0004] For example, a p-type transistor device can be formed by selecting a semiconductive material which is efficient at accepting, conducting, and donating holes, and selecting a material for the source and drain electrodes which is efficient at injecting and accepting holes from the semiconductive material. Good energy-level matching of the Fermi-level in the electrodes with the HOMO level of the semiconductive material can enhance hole injection and acceptance. In contrast, an n-type transistor device can be formed by selecting a semiconductive material which is efficient at accepting, conducting, and donating electrons, and selecting a material for the source and drain electrodes which is efficient at injecting electrons into, and accepting electrons from, the semiconductive material. Good energy-level matching of the Fermi-level in the electrodes with the LUMO level of the semiconductive material can enhance electron injection and acceptance. Transistors can be formed by depositing the components in thin films to form a thin film transistor (TFT). When an organic material is used as the semiconductive material in such a device, it is known as an organic thin film transistor (OTFT).

[0005] OTFTs may be manufactured by low cost, low temperature methods such as solution processing. Moreover, OTFTs are compatible with flexible plastic substrates, offering the prospect of large-scale manufacture of OTFTs on flexible substrates in a roll-to-roll process.

[0006] With reference to Figure 2, the general architecture of a bottom-gate organic thin film transistor (OTFT) comprises a gate electrode 12 deposited on a substrate 10. An insulating layer 11 of dielectric material is deposited over the gate electrode 12 and source and drain electrodes 13, 14 are deposited over the insulating layer 11 of dielectric material. The source and drain electrodes 13, 14 are spaced apart to define a channel region therebetween located over the gate electrode 12. An organic semiconductor (OSC) material 15 is deposited in the channel region for connecting the source and drain electrodes 13, 14. The OSC material 15 may extend at least partially over the source and drain electrodes 13, 14.

[0007] Alternatively, it is known to provide a gate electrode at the top of an organic thin film transistor to form a so-called top-gate organic thin film transistor. In such an architecture, source and drain electrodes are deposited on a substrate and spaced apart to define a channel region there between. A layer of an organic semiconductor material is deposited in the channel region to connect the source and drain electrodes and may extend at least partially over the source and drain electrodes. An insulating layer of dielectric material is deposited over the organic semiconductor material and may also extend at least partially over the source and drain electrodes. A gate electrode is deposited over the insulating layer and located over the channel region.

[0008] An organic thin film transistor can be fabricated on a rigid or flexible substrate. Rigid substrates may be selected from glass or silicon and flexible substrates may comprise thin glass or plastics such as poly(ethylene-terephthalate) (PET), poly(ethylene-naphthalate) (PEN), polycarbonate and polyimide.

[0009] The organic semiconductive material may be made solution processable through the use of a suitable solvent. Exemplary solvents include mono- or poly-alkylbenzenes such as toluene and xylene; tetralin; and chloroform. Preferred solution deposition techniques include spin coating and ink jet printing. Other solution deposition techniques include dip-coating, roll printing and screen printing.

[0010] The length of the channel defined between the source and drain electrodes may be up to 500 microns, but preferably the length is less than 200 microns, more preferably less than 100 microns, most preferably less than 20 microns.

[0011] The gate electrode can be selected from a wide range of conducting materials for example a metal (e.g. gold) or metal compound (e.g. indium tin oxide). Alternatively, conductive polymers may be deposited as the gate electrode. Such conductive polymers may be deposited from solution using, for example, spin coating or ink jet printing techniques and other solution deposition techniques discussed above.

[0012] The insulating layer comprises a dielectric material selected from insulating materials having a high resistivity. The dielectric constant, k, of the dielectric is typically around 2-3 although materials with a high value of k are desirable because the capacitance that is achievable for an OTFT is directly proportional to k, and the drain current ID is directly proportional to the capacitance. Thus, in order to achieve high drain currents with low operational voltages, OTFTs with thin dielectric layers in the channel region are preferred.

[0013] The dielectric material may be organic or inorganic. Preferred inorganic materials include SiO2, SiNx and spin-on-glass (SOG). Preferred organic materials are generally polymers and include insulating polymers such as poly vinylalcohol (PVA), polyvinylpyrrolidine (PVP), acrylates such as polymethylmethacrylate (PMMA), fluorinated polymers and benzocyclobutanes (BCBs) available from Dow Corning. The insulating layer may be formed from a blend of materials or comprise a multi-layered structure.

[0014] The dielectric material may be deposited by thermal evaporation, vacuum processing or lamination techniques as are known in the art. Alternatively, the dielectric material may be deposited from solution using, for example, spin coating or ink jet printing techniques and other solution deposition techniques discussed above.

[0015] If the dielectric material is deposited from solution onto the organic semiconductor, it should not result in dissolution of the organic semiconductor. Likewise, the dielectric material should not be dissolved if the organic semiconductor is deposited onto it from solution. Techniques to avoid such dissolution include: use of orthogonal solvents for example use of a solvent for deposition of the uppermost layer that does not dissolve the underlying layer; and cross linking of the underlying layer.

[0016] The thickness of the insulating layer is preferably less than 2 micrometres, more preferably less than 500 nm.

[0017] Organic semiconductors are a class of organic molecules having extensively conjugated pi systems allowing for the movement of electrons.

[0018] Preferred methods for preparation of these molecules are Suzuki reactions (coupling or polymerisation reactions) as described in, for example, WO 2000/53656 and Yamamoto polymerisation as described in, for example, T. Yamamoto, "Electrically Conducting And Thermally Stable pi-Conjugated Poly(arylene)s Prepared by Organometallic Processes", Progress in Polymer Science 1993, 17, 1153-1205. These techniques both operate via a "metal insertion" wherein the metal atom of a metal complex catalyst is inserted between an aryl group and a leaving group of a monomer. In the case of Yamamoto polymerisation, a nickel complex catalyst is used; in the case of Suzuki reaction, a palladium complex catalyst is used.

[0019] For example, in the synthesis of a linear polymer by Yamamoto polymerisation, a monomer having two reactive halogen groups is used. Similarly, according to the method of Suzuki reaction, at least one reactive group is a boron derivative group such as a boronic acid or boronic ester and the other reactive group is a halogen. Preferred halogens are chlorine, bromine and iodine, most preferably bromine.

[0020] Alternatively, stannyl groups may be used as reactive groups in polymerisation or coupling reactions (Stille reactions).

[0021] The performance of organic semiconductors is typically assessed by measurement of its "charge mobility" (cm2 V-1s-1), which may relate to either the mobility of holes or electrons. This measurement relates to the drift velocity of charge carriers to an applied electric field across a material.

[0022] Organic semiconductors having relatively high mobilities tend to be those which comprise compounds having a rigid planar structure with extensive conjugation which allows for efficient and effective pi-pi stacking in the solid state.

[0023] WO 2007/068618 describes a variety of organic semiconductors, each comprising an array of fused aromatic rings having a central benzene ring substituted with acetylene groups.

[0024] JP 2007/088222 and WO 2007/116660 describe the use of benzodithiophenes and its derivatives in small molecule, oligomeric and polymeric form, as organic semiconductors.

[0025] Scherf et al. in Journal of Polymer Science A: Polymer Chemistry 46(22) 7342 to 7353 describe polymers having the structure:



[0026] However, the increased level of conjugation required to allow compounds to form such a pi-pi stack may also result in a decrease in band gap and stability of the semiconductor, leading to poor performance and a short lifetime. Moreover, these compounds may be highly insoluble due to the size of molecule required to achieve extended conjugation, which poses particular problems in synthesis and renders their use in efficient transistor production methods, such as ink-jet printing, difficult.

[0027] The present invention seeks to provide an organic semiconductor having high mobility, good solubility and good ambient stability.

[0028] In a first aspect, the present invention provides a semiconducting compound. The compound preferably comprises the structure:

where R1 to R4 independently comprise, but are not limited to, optionally substituted straight, branched or cyclic alkyl chains having between 2 and 20 carbon atoms (preferably 2 to 12 carbon atoms, or 2 to 6 carbon atoms), alkoxy, amino, amido, silyl, alkyl, alkenyl, aryl or hetero aryl;

where X1 and X2 independently comprise S, O, , NR5 or SiR6R7 where R5 to R7 independently comprise C1 to C5 branched, straight or cyclic alkyl chains;

where Ar1 comprises a heterocyclic aromatic ring, and where n is an integer between 1 and 4.



[0029] While solubilising groups can be placed anywhere on the structure, the inventors have found that the preferable positioning of solubilising groups at the "bridge head" positions on five membered rings adjacent the central ring or rings provides a greater solubilising effect than when positioned at the periphery of the molecule.

[0030] Accordingly, shorter and/or smaller solubilising groups may be used at the bridge head position. These shorter and/or smaller solubilising groups are less able to interfere with Π-Π stacking, thereby potentially providing improved mobility in addition to improved solution processability.

[0031] Moreover, the improved solubility afforded by the positioning of the solubilising groups allows the planar conjugated structure of the semiconducting species to be further extended while the species remains soluble.

[0032] Preferably, the semiconducting compound comprises the structure:

where Ar2 is a homocyclic or heterocyclic aromatic ring. Where Ar2 is a heterocyclic aromatic ring, it preferably comprises at least one heteroatom selected from the group S, O, NR5 or SiR6R7.

[0033] Preferably, the compound comprises one or more further aromatic groups fused in series to Ar1 and/or, if present, Ar2. One, some, or all of said further aromatic groups may be, and in some embodiments are, heterocyclic groups containing at least one heteroatom selected from the group S, O, NR5 or SiR6R7.

[0034] Preferably one or both of the terminal aryl or heteroaryl groups of the compound is substituted with one or more substituents T, at least one of which groups comprises a reactive or polymerisable group or optionally substituted straight, branched or cyclic alkyl chains having 1 to 20 (e.g. 1 to 12) carbon atoms, alkoxy, amino, amido, silyl, alkyl, alkenyl, aryl or hetero aryl, the remaining groups, if any,independently comprising hydrogen or optionally substituted straight, branched or cyclic alkyl chains having 1 to 20 (e.g. 1 to 12) carbon atoms, alkoxy, amino, amino, amido, silyl, alkyl, or alkenyl.

[0035] The reactive polymer group or groups preferably independently comprise such moieties as halogens, boronic acids, diboronic acids, esters of boronic and diboronic acids, alkylene groups or stannyl groups.

[0036] The terminal aryl groups represent aryl groups fused to just one other aryl or heroaryl group, for example, group Ar1 and the group containing heteroatom X1 in structure I and groups Ar1 and Ar2 in structure II.

[0037] Preferably the compound comprises a structure selected from the group:







[0038] Where X3 to X6 may independently comprise S, O, NR5 or SiR6R7, and where if any of X3 to X6 is part of a terminal aryl group, X3 to X6, if present, may comprise C2H2.

[0039] Alternatively, the compound may comprise the structure:

where one or more of the optional aryl groups Ar1 to Ar6 independently comprises a heterocycle including at least one heteroatom selected from the groups: S, O, NR5 or SiR6R7.

[0040] Preferably one or both of the terminal aryl groups comprise homocyclic rings.

[0041] R1 to R4 may be the same or different, and preferably independently comprise optionally substituted straight branched or cyclic alkyl chains having between 2 and 12 carbon atoms, more preferably between 2 and 6 carbon atoms.

[0042] In another aspect, the invention provides an electronic device comprising a semiconducting portion comprising a compound described herein.

[0043] In another aspect, the invention provides a solution for applying to the surface of a substrate to form a semiconducting portion on the substrate, the solution comprising a compound as described herein.

[0044] In a further aspect, the invention provides a method of manufacturing an electronic device comprising applying a solution as described herein onto a substrate.

Figure 1 shows a synthesis of a compound according to the invention.

Figure 2 is a schematic diagram of a general architecture of a bottom-gate organic thin film transistor according to the prior art;

Figure 3 is a schematic diagram of a pixel comprising an organic thin film transistor and an adjacent organic light emitting device fabricated on a common substrate according to an embodiment of the present invention; and,

Figure 4 is a schematic diagram of an organic thin film transistor fabricated in a stacked relationship to an organic light emitting device according to an embodiment of the present invention.



[0045] Throughout the following description like reference numerals shall be used to identify like parts.

[0046] Organic semiconductors according to the present invention may be manufactured by means of a Suzuki-type cross-coupling reaction of a pinacol boronate of a thienothiophene with a diethyl-2,5-dibromoterephthalate in the presence of Pd(PPh3)4 and K2CO3 to give a diketo compound. Further reaction with methyl lithium followed by a BF3·Et2O-mediated cyclization affords the compounds of the invention as shown in Figure 1.

[0047] Other compounds which may be manufactured by this method are shown below:





















































[0048] The resulting compounds are easily soluble and may thus be applied by ink-jet printing or other suitable solution deposition technique onto a substrate to provide the semiconducting layer 15 in a thin film transistor such as is shown in Figure 2.

[0049] An application of such an organic thin film transistor (OTFT) may be to drive pixels in an optical device, preferably an organic optical device. Examples of such optical devices include photoresponsive devices, in particular photodetectors, and light-emissive devices, in particular organic light emitting devices. OTFTs are particularly suited for use with active matrix organic light emitting devices, e.g. for use in display applications.

[0050] Figure 3 shows a pixel comprising an organic thin film transistor 100 and an adjacent organic light emitting device (OLED) 102 fabricated on a common substrate 104. The OTFT 100 comprises gate electrode 106, dielectric layer 108, source and drain electrodes 110 and 112 respectively, and OSC layer 114. The OLED 102 comprises anode 116, cathode 118 and an electroluminescent layer 120 provided between the anode 116 and cathode 118. Further layers may be located between the anode 116 and cathode 118, such as charge transporting, charge injecting or charge blocking layers. In the embodiment of Figure 3, the layer of cathode material 118 extends across both the OTFT 100 and the OLED 102, and an insulating layer 122 is provided to electrically isolate the cathode layer 118 from the OSC layer 122. The active areas of the OTFT 100 and the OLED 102 are defined by a common bank material formed by depositing a layer of photoresist 124 on substrate 104 and patterning it to define OTFT 100 and OLED 102 areas on the substrate.

[0051] In Figure 3, the drain electrode 112 is directly connected to the anode 116 of the organic light emitting device 102 for switching the organic light emitting device 102 between emitting and non-emitting states.

[0052] In an alternative arrangement illustrated in Figure 4, an organic thin film transistor 200 may be fabricated in a stacked relationship to an organic light emitting device 202. In such an embodiment, the organic thin film transistor 202 is built up as described above in either a top or bottom gate configuration. As with the embodiment of Figure 3, the active areas of the OTFT 200 and OLED 202 are defined by a patterned layer of photoresist 124, however in this stacked arrangement, there are two separate bank layers 124 - one for the OLED 202 and one for the OTFT 200. A planarisation layer 204 (also known as a passivation layer) is deposited over the OTFT 200. Exemplary passivation layers 204 include BCBs and parylenes. The organic light emitting device 202 is fabricated over the passivation layer 204 and the anode 116 of the organic light emitting device 202 is electrically connected to the drain electrode 112 of the OTFT 200 by a conductive via 206 passing through passivation layer 204 and bank layer 124.

[0053] It will be appreciated that pixel circuits comprising an OTFT and an optically active area (e.g. light emitting or light sensing area) may comprise further elements. In particular, the OLED pixel circuits of Figures 35 and 4 will typically comprise least one further transistor in addition to the driving transistor shown, and at least one capacitor. It will be appreciated that the organic light emitting devices described herein may be top or bottom-emitting devices. That is, the devices may emit light through either the anode or cathode side of the device. In a transparent device, both the anode and cathode are transparent. It will be appreciated that a transparent cathode device need not have a transparent anode (unless, of course, a fully transparent device is desired), and so the transparent anode used for bottom-emitting devices may be replaced or supplemented with a layer of reflective material such as a layer of aluminium.

[0054] Transparent cathodes are particularly advantageous for active matrix devices because emission through a transparent anode in such devices may be at least partially blocked by OTFT drive circuitry located underneath the emissive pixels as can be seen from the embodiment illustrated in Figure 4.

[0055] Thicknesses of the gate electrode, source and drain electrodes may be in the region of 5 - 200nm, although typically 50nm as measured by Atomic Force Microscopy (AFM), for example.

[0056] Other layers may be included in the device architecture. For example a self assembled monolayer (SAM) may be provided on the gate, source or drain electrodes, and/or one may be provided on the substrate, insulating layer and organic semiconductor material to promote crystallinity, reduce contact resistance, repair surface characteristics and promote adhesion where required. In particular, the dielectric surface in the channel region may be provided with a monolayer comprising a binding region and an organic region to improve device performance, e.g. by improving the organic semiconductor's morphology (in particular polymer alignment and crystallinity) and covering charge traps, in particular for a high k dielectric surface. Exemplary materials for such a monolayer include chloro- or alkoxy-silanes with long alkyl chains, e.g. octadecyltrichlorosilane.

[0057] No doubt many other effective alternatives will occur to the skilled person. It will be understood that the invention is not limited to the described embodiments and encompasses modifications apparent to those skilled in the art lying within the scope of the claims appended hereto.


Claims

1. A semiconducting compound comprising the structure:

where:

R1 to R4 independently comprise: optionally substituted straight, branched or cyclic alkyl chains having between 2 and 20 carbon atoms; an alkoxy group; an amino group; an amido group; a silyl group; an alkyl group; an alkenyl group; an aryl group; or a hetero aryl group;

X1 and X2 independently are S, O, NR5 or SiR6R7, wherein R5 to R7 independently comprise C1 to C5 branched, straight or cyclic alkyl chains;

Ar1 is a heterocyclic aromatic ring;

Ar2 is a homo-cyclic or heterocyclic aromatic ring; and

n is an integer between 1 and 4.


 
2. A semiconducting compound according to claim 1, wherein X1 and X2 independently comprise S, O or NR5, wherein R5 comprises C1 to C5 branched, straight or cyclic alkyl chains.
 
3. A semiconducting compound according to claim 1 or claim 2, wherein Ar2 is a heterocyclic aromatic ring.
 
4. A semiconducting compound according to any of the preceding claims, wherein the semiconducting compound comprises one or more further aromatic groups fused in series to Ar1 and/or Ar2.
 
5. A semiconducting compound according to claim 4, wherein at least one of said further aromatic groups comprises a heterocyclic group.
 
6. A semiconducting compound according to any of the preceding claims, wherein one or both terminal aryl groups of the semiconducting compound is substituted with one or more groups T, wherein at least one of the groups T comprises: an optionally substituted straight, branched or cyclic alkyl chain having 1 to 20 carbon atoms; an alkoxy group; an amino group; an amido group; a silyl group; an alkyl group; an alkenyl group; an aryl group; or a hetero aryl group.
 
7. A semiconducting compound according to claim 6, wherein remaining groups T independently comprise: hydrogen; optionally substituted straight, branched or cyclic alkyl chains having 1 to 20 carbon atoms, an alkoxy group, an amino group, an amido group, a silyl group, an alkyl group, or an alkenyl group.
 
8. A semiconducting compound according to claim 6 or claim 7, wherein the semiconducting compound comprises a structure selected from the group:





wherein:
X to X6 independently are S, O, NR5 or SiR6R7, and where any of X3 to X6 is part of a terminal aryl group, and X3 to X6, if present, preferably comprise C2H2.
 
9. A semiconducting compound comprising the structure:

where:

R1 to R4 independently comprise: substituted straight, branched or cyclic alkyl chains having between 2 and 20 carbon atoms; an alkoxy group; an amino group; an amido group; a silyl group; an alkyl group; an alkenyl group; an aryl group; or a hetero aryl group;

X1 and X2 independently are S, O, NR5 or SiR6R7, wherein R5 to R7 independently comprise C1 to C5 branched, straight or cyclic alkyl chains;

T1 and T2 independently comprise optionally substituted straight, branched or cyclic alkyl chains having 1 to 20 carbon atoms, an alkoxy group, an amino group, an amido group, a silyl group, an alkyl group, an alkenyl group, an aryl group or a heteroaryl group;
Ar1 is a heterocyclic aromatic ring;

one or more of the optional aryl groups Ar2 to Ar6 independently comprise a heterocycle; and

n is an integer between 1 and 4.


 
10. A semiconducting compound according to claim 9, wherein one or both terminal aryl groups comprise homocyclic rings.
 
11. A semiconducting compound as claimed in any of the preceding claims, wherein at least one of R1 to R4 comprises optionally substituted straight, branched or cyclic alkyl chains having between 2 and 12 carbon atoms.
 
12. A semiconducting compound according to claim 11, wherein at least one of R1 to R4 comprises optionally substituted straight, branched or cyclic alkyl chains having between 2 and 6 carbon atoms.
 
13. An electronic device, comprising a semiconducting compound according to any of the preceding claims.
 
14. A solution for applying to a surface of a substrate to form a semiconducting portion on the substrate, the solution comprising a semiconducting compound according to any one of claims 1 to 12.
 
15. A method of manufacturing an electronic device comprising applying a solution according to claim 14 to a substrate.
 




Drawing




















REFERENCES CITED IN THE DESCRIPTION



This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description




Non-patent literature cited in the description