Improvements in and relating to organic semiconducting layers

Improvements in and related organic semiconducting layers

The present invention relates to an organic semiconducting layer formulation, a layer containing the formulation, a method for preparing the formulation and the layer, and electronic components (including an organic field-effect transistor (OFET)) containing the formulation and the layer.

In recent years, organic semiconducting materials have been developed to manufacture more diverse and lower-cost electronic components. These materials can be applied to a wide range of components or devices, including, for example, organic field-effect transistors (OFET), organic light-emitting diodes (OLED), photodetectors, photovoltaic (PV) cells, sensors , Memory components and logic circuits. Organic semiconducting materials are typically present in electronic components in the form of thin layers (for example, less than 1 micron thick).

Fives<img file="TW200529483A_D0001.tif" />It has been proved to be an organic semiconducting material. Fives<img file="TW200529483A_D0002.tif" />It has been described as requiring a highly crystalline structure to provide molecular orientation that produces good charge mobility. Therefore, in the previous art, partly due to the five<img file="TW200529483A_D0003.tif" />The fact that it is quite insoluble in general solvents, so five<img file="TW200529483A_D0004.tif" />The film is vapor deposited. However, vapor deposition requires expensive and complicated equipment. In view of the latter problem, a method of coating includes five<img file="TW200529483A_D0005.tif" />The solution of the precursor, and then the precursor compound is chemically transformed (for example, by heat) into five<img file="TW200529483A_D0006.tif" />. However, the latter method is also complicated, and it is difficult to control to obtain the regular structure required for good charge mobility.

Soluble five<img file="TW200529483A_D0007.tif" />Compounds have recently been described as organic semiconducting compounds in the prior art, see, for example, US 2003/0116755 A (Takahashi) and US 6,690,029 (Anthony). WO 03/016599 (Asahi) recommends the use of five in FET<img file="TW200529483A_D0008.tif" />, Which will dissolve five<img file="TW200529483A_D0009.tif" />The solution is deposited on the substrate, and the solvent is evaporated to form five<img file="TW200529483A_D0010.tif" />Membrane. The film. However, US 6,690,029 and WO 03/016599 state that it can dissolve five<img file="TW200529483A_D0011.tif" />A highly crystalline structure is still required in thin films to obtain acceptable charge mobility, especially when used in FETs, which means five<img file="TW200529483A_D0012.tif" />It still has to be deposited in a controlled manner. Therefore, the prior art is careful not to dilute the five in any way<img file="TW200529483A_D0013.tif" />, Otherwise it is expected that it will destroy the five<img file="TW200529483A_D0014.tif" />The crystalline structure, and therefore reduce the charge mobility.

Improved charge mobility is one of the goals of novel electronic components. Another goal is to improve the stability and integrity of the organic semiconductor layer. One way that has the potential to improve the stability and integration of the organic semiconductor layer in the device is to include organic semiconducting components in an organic binder. However, when the organic semiconducting component is combined with the binder, it is effectively "diluted" by the binder, and a decrease in charge mobility can be expected. Especially diluting organic semiconductors by mixing with adhesives will destroy the molecular rules in the semiconducting layer. For example, the organic semiconducting components in the channels of OFETs are particularly problematic, because it is expected that any damage to the orbital overlap between the molecules immediately adjacent to the gate insulator (the first few molecular layers) will reduce the mobility. The electrons or holes are then forced to extend their paths into the whole organic semiconductor, which is an undesirable result. It is expected that certain organic semiconducting materials are more susceptible to the influence of the use of adhesives than other materials. Due to five<img file="TW200529483A_D0015.tif" />It has been taught that a highly regular structure is required to obtain a useful charge mobility, so the need to use five<img file="TW200529483A_D0016.tif" />Contains binder. WO 03/030278 (Philips) tried to use an adhesive, but it showed that it should be (precursor) five<img file="TW200529483A_D0017.tif" />With increasing amount of adhesive, even when mixed with less than 5% of adhesive, the FET mobility will gradually decrease.

WO 02/45184 (Avecia) describes specific low-polarity binder resins used in FETs with organic semiconductors. However, when the semiconductor is diluted in the adhesive, a decrease in charge mobility can also be expected.

The purpose of the present invention is to reduce or overcome the shortcomings in the organic semiconducting layer as described above.

According to the first aspect of the present invention, there is provided an organic semiconducting layer formulation, which contains a permittivity of 3.3 or less at 1,000 hertz (Hz)<img file="TW200529483A_D0018.tif" />Organic binder; and chemical formula A<img file="TW200529483A_D0019.tif" />Compound:<chemistry general="n"><img file="TW200529483A_D0020.tif" /></chemistry>Where R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁And R₁₂Each can be the same or different, and each represents hydrogen; C is substituted if necessary₁-C₄₀Carbyl or hydrocarbyl; optionally substituted C₁-C₄₀Alkoxy; optionally substituted C₆-C₄₀Aryloxy; optionally substituted C₇-C₄₀Alkylaryloxy; optionally substituted C₂-C₄₀Alkoxycarbonyl; optionally substituted C₇-C₄₀Aryloxycarbonyl; Cyano (-CN); Carboxamide (-C(=O)NH₂); haloformyl group (-C(=O)-X, where X represents a halogen atom); formyl group (-C(=O)-H); isocyanate group; isocyanate group; thiocyanate group or Thioisocyanate group; optionally substituted amine group; hydroxyl group; nitro group; CF₃Group; halo (Cl, Br, F); or optionally substituted silyl group; and R₂And R₃And/or R₈And R₉Each pair can be bridged to form C₄-C₄₀Saturated or unsaturated ring, this saturated or unsaturated ring can be through oxygen atom, sulfur atom or by chemical formula -N(R_a)-(Where R_aIs a hydrogen atom or optionally substituted hydrocarbyl group) inserted into the group, or optionally substituted; and many of them<img file="TW200529483A_D0021.tif" />One or more of the carbon atoms in the structure can be substituted by heteroatoms selected from N, P, As, O, S, Se, and Te as needed;<img file="TW200529483A_D0022.tif" />Substituents R on adjacent ring positions₁-R₁₂Any two or more of, as required, can be formed together separately, as required, can be passed O, S or -N(R_a) (Where R_a(As defined above) another interrupt C₄-C₄₀Saturated or unsaturated ring or fused at most<img file="TW200529483A_D0023.tif" />The aromatic ring system; and where n is 0, 1, 2, 3 or 4, n is 0, 1 or 2 preferably, and n is 0 or 2 is the best, that is more<img file="TW200529483A_D0024.tif" />Compound five<img file="TW200529483A_D0025.tif" />Compound (n=2) or "false five<img file="TW200529483A_D0026.tif" />"(N=0) compound.

Fives<img file="TW200529483A_D0027.tif" />The compound is preferably a compound selected from any one of compound groups 1 to 9 or its isomers, wherein:<b>Compound group 1 is represented by chemical formula 1:</b><chemistry general="n"><img file="TW200529483A_D0028.tif" /></chemistry><b>Compound group 2 is represented by chemical formula 2:</b><chemistry general="n"><img file="TW200529483A_D0029.tif" /></chemistry><b>Compound group 3 is represented by chemical formula 3:</b><chemistry general="n"><img file="TW200529483A_D0030.tif" /></chemistry><b>Compound group 4 is represented by chemical formula 4:</b><chemistry general="n"><img file="TW200529483A_D0031.tif" /></chemistry><b>Compound group 5 is represented by chemical formula 5:</b><chemistry general="n"><img file="TW200529483A_D0032.tif" /></chemistry><b>Compound group 6 is represented by chemical formula 6:</b><chemistry general="n"><img file="TW200529483A_D0033.tif" /></chemistry><b>Compound group 7 is represented by chemical formula 7:</b><chemistry general="n"><img file="TW200529483A_D0034.tif" /></chemistry><b>Compound group 8 is represented by chemical formula 8:</b><chemistry general="n"><img file="TW200529483A_D0035.tif" /></chemistry><b>Compound group 9 is represented by chemical formula 9:</b><chemistry general="n"><img file="TW200529483A_D0036.tif" /></chemistry>And R in the case of compound group 1₆And R₁₃, R in the case of compound group 2₅And R₁₄, R in the case of compound group 3₂, R₃, R₉And R₁₀, R in the case of compound group 4₂And R₃, R in the case of compound group 5₂, R₃, R₁₁And R₁₂, R in the case of compound group 6₂And R₉, R in the case of compound group 7₅, R₇, R₁₂And R₁₄, R in the case of group 8₁, R₂, R₃, R₄, R₈, R₉, R₁₀, R₁₁, R₁₅, R₁₆, R₁₇And R₁₈, And R in the case of group 9₂, R₃, R₇, R₈, R₁₅, R₁₆, R₁₇Each can be the same or different, and each represents: H; C replaced as necessary₁-C₄₀Carbon group or hydrocarbyl group; optionally substituted C₁-C₄₀Alkoxy; optionally substituted C₆-C₄₀Aryloxy; optionally substituted C₇-C₄₀Alkylaryloxy; optionally substituted C₂-C₄₀Alkoxycarbonyl; optionally substituted C₇-C₄₀Aryloxycarbonyl; Cyano (-CN); Carboxamide (-C(=O)NH₂); haloformyl group (-C(=O)-X, where X represents a halogen atom); formyl group (-C(=O)-H); isocyanate group; isocyanate group; thiocyanate group or Thioisocyanate group; optionally substituted amine group; hydroxyl group; nitro group; CF₃Group; halo (Cl, Br, F); or optionally substituted silyl group; and R₁And R₂, R₂And R₃, R₃And R₄, R₈And R₉, R₉And R₁₀, R₁₀And R₁₁, R₁₅And R₁₆And R₁₆And R₁₇Each of the pairs can be bridged to each other to form C₄-C₄₀Saturated or unsaturated ring, this saturated or unsaturated ring can be through oxygen atom, sulfur atom or chemical formula: -N(R_a)-(Where R_aThe group represented by hydrogen atom or hydrocarbon group) is inserted, or it can be substituted if necessary; and A represents silicon or germanium.

The "R" substituent in compound groups 1-9 (i.e., R₁, R₂Etc.) Department of instruction is named according to the fifth<img file="TW200529483A_D0037.tif" />Substituents at the position:<chemistry general="n"><img file="TW200529483A_D0038.tif" /></chemistry>

It has now been surprisingly and advantageously found that according to the present invention, the specified soluble more<img file="TW200529483A_D0039.tif" />Compounds, especially from compound groups 1-9 of 5<img file="TW200529483A_D0040.tif" />Compound (hereinafter often referred to as "multiple<img file="TW200529483A_D0041.tif" />"), combined with organic binder resin (hereinafter sometimes referred to as "binder") can lead to more<img file="TW200529483A_D0042.tif" />There is little or no decrease in the charge mobility rate, and even an increase in it in some cases. For example, it can dissolve more<img file="TW200529483A_D0043.tif" />Dissolved in a binder resin (such as poly(α-methylstyrene)) and deposited (such as by spin coating) to form, for example, 0.5-1.5 cm²/volt/second (cm²V^-1s^-1) The organic semiconducting layer with high charge mobility. Since the previous skill teaching has resulted in such a high rate of movement, it is expected to be more<img file="TW200529483A_D0044.tif" />Compounds require strong molecular rules, so this result is particularly unexpected. In FETs, it is expected that dilution in the adhesive will produce at least an order of magnitude reduction in mobility. It is also surprising to find that even if it is tied to the adhesive: more<img file="TW200529483A_D0045.tif" />Under the ratio of 1:1, the movement rate is also much higher than that of pure use alone.<img file="TW200529483A_D0046.tif" />The compound is comparable. Therefore, the results produced by the present invention are surprising in the following aspects: a) the mobility rate is maintained despite the possibility of breaking the molecular rules, and b) the mobility rate is maintained despite the expected increase in the intermolecular distance. At the same time, the semiconducting layer formed therefrom exhibits excellent film-forming properties and is particularly stable.

In a preferred embodiment of the present invention, there is provided an organic semiconducting layer formulation used in organic field effect transistors, which includes compounds selected from compound groups 1 to 9, with groups 1 and 8 being more preferred; bonding Agents; and solvents as needed.

In a particularly preferred embodiment of the present invention, there is provided an organic semiconducting layer formula used in organic field effect transistors, which includes a compound of formula 1; a binder; and a solvent,<chemistry general="n"><img file="TW200529483A_D0047.tif" /></chemistry>

The adhesive is selected from poly(α-methylstyrene), Topas^TM 8007, poly(4-methylstyrene), polystyrene and polystyrene-co-α-methylstyrene, poly(α-methylstyrene) is the best; and the solvent is selected from toluene, ethyl Cyclohexane, methoxybenzene and p-xylene; toluene is the best.

In a more particularly preferred embodiment of the present invention, there is provided an organic semiconducting layer formulation used in organic field effect transistors, which includes a compound of formula 2; a binder; and a solvent,<chemistry general="n"><img file="TW200529483A_D0048.tif" /></chemistry>

Among them, the binder is selected from poly(α-methylstyrene), polyvinyl cinnamate, and poly(4-vinyl biphenyl), poly(α-methylstyrene) is the best; and solvent system 1,2-Dichlorobenzene.

In another more particularly preferred embodiment of the present invention, an organic semiconducting layer formulation used in organic field effect transistors is provided, which includes a compound of Chemical Formula 3; a binder; and a solvent,<chemistry general="n"><img file="TW200529483A_D0049.tif" /></chemistry>

Wherein n and m are each 0, 1, 2, 3, or 4, preferably 0, 1, or 2; the binder is poly(α-methylstyrene); and the solvent is toluene.

Once through more<img file="TW200529483A_D0050.tif" />Combining with adhesives to produce a high mobility organic semiconducting layer formulation, the resulting formulation can achieve several other advantages. For example, due to<img file="TW200529483A_D0051.tif" />The system is soluble, so it can be in liquid form, for example, deposited from a solution. With the additional use of adhesives, it has now been found that the formula can be applied to a large area in a highly uniform manner. If no adhesive is used, more<img file="TW200529483A_D0052.tif" />Since it cannot produce a uniform film, it cannot be spin-coated on a large area. In the previous art, spin coating and drop-casting are more pure<img file="TW200529483A_D0053.tif" />The layer may have a relatively high mobility in some cases, but it is difficult to provide a large-area film with a constant mobility on the entire substrate (this is a specific requirement for electronic components). In addition, when the adhesive is used in the formulation, the properties of the formulation (such as viscosity, solid content, surface tension) can be controlled to adjust the printing process. Although not wishing to be bound by any particular theory, it is also expected that the use of binders in the formulation can fill the volume between the crystal grains that would otherwise be voids, and make the organic semiconducting layer less sensitive to air and moisture . For example, the layer formed according to the first aspect of the present invention exhibits very good stability in the air in the OFET device.

The present invention also provides an organic semiconducting layer containing the organic semiconducting layer formulation.

The present invention further provides a method of preparing an organic semiconducting layer, which comprises: (i) including as many as previously described in the text<img file="TW200529483A_D0054.tif" />A liquid layer of a mixture of a compound, an organic binder resin or its precursor, and an optional solvent is deposited on the substrate; and (ii) a solid layer of the organic semiconducting layer is formed from the liquid layer. This method is explained in more detail below.

The present invention also provides an electronic device including the organic semiconducting layer. This electronic component may include, but is not limited to, organic field-effect transistors (OFET), organic light-emitting diodes (OLED), photodetectors, sensors, logic circuits, memory components, capacitors or photovoltaics (PV )Battery. For example, the active semiconductor channel between the drain and the source in the OFET can include the layer of the present invention. Another example is that the charge (hole or electron) injection or transport layer in the OLED device may include the layer of the present invention. The formulation according to the present invention and the layers formed therefrom are particularly useful for OFETs, especially in terms of the preferred embodiments described herein. US 2003/0116755 A and US 6,690,029 illustrate specific multiple<img file="TW200529483A_D0055.tif" />Compound, and the disclosed therein can be used to synthesize multiple<img file="TW200529483A_D0056.tif" />The method is used in the present invention to produce as many as described in the text<img file="TW200529483A_D0057.tif" />Compound. US 3,557,233 (American Cyanamid) also stated<img file="TW200529483A_D0058.tif" />Methods. The method. Can be used to synthesize many according to the present invention<img file="TW200529483A_D0059.tif" />Alternative methods of compounds within the skills and knowledge of skilled artisans are disclosed in Organic Letters 2004, Vol. 6, No. 10, pages 1609-1612.

Now, the compound groups 1-9 will be described in more detail.

<b>Compound group 1</b>

Compound group 1 is represented by chemical formula 1:<chemistry general="n"><img file="TW200529483A_D0060.tif" /></chemistry>In compound group 1 of 5<img file="TW200529483A_D0061.tif" />Among the derivatives, R₆And R₁₃Each is the same or different, and each includes C which is substituted as necessary₁-C₄₀Carbon group or hydrocarbon group. R₆And R₁₃Groups include optionally substituted, optionally unsaturated C₁-C₄₀Carbon group or hydrocarbyl group, such as optionally substituted alkenyl, alkynyl, aryl, etc., is more preferred (optionally substituted alkynyl is a preferred group, especially optionally substituted ethynyl). R₆And R₁₃Substituent system and five<img file="TW200529483A_D0062.tif" />The ring structure is preferably π-conjugated. However, R₆And R₁₃The groups preferably contain the same substituents as each other. In compound group 1 of 5<img file="TW200529483A_D0063.tif" />Among the derivatives, in the fifth place except the 6 and 13 positions<img file="TW200529483A_D0064.tif" />The ring positions on are preferably unsubstituted, that is, they are occupied by hydrogen.

Examples of compound group 1 are as follows:<chemistry general="n"><img file="TW200529483A_D0065.tif" /></chemistry><chemistry general="n"><img file="TW200529483A_D0066.tif" /></chemistry>

Where Ra includes C which is replaced as necessary_1-40Carbon group or hydrocarbon group, optionally substituted C_1-10Alkyl is more preferred; and n is 0, 1, 2, 3, 4 or 5, 1, 2 or 3 is most preferred.

<b>Compound group 2</b>

Compound group 2 is represented by chemical formula 2:<chemistry general="n"><img file="TW200529483A_D0067.tif" /></chemistry>In compound group 2 of 5<img file="TW200529483A_D0068.tif" />Among the derivatives, R₅And R₁₄Each is the same or different, and each includes C which is substituted as necessary₁-C₄₀Carbon group or hydrocarbon group. R₅And R₁₄The group includes optionally substituted unsaturated C₁-C₄₀Carbon group or hydrocarbyl group, such as optionally substituted alkenyl, alkynyl, aryl, aralkyl group is more preferred (optionally substituted alkynyl group is preferred, especially optionally substituted ethynyl group). R₅And R₁₄Substituent system and five<img file="TW200529483A_D0069.tif" />The ring structure is preferably π-conjugated. However, R₅And R₁₄It is best to include the same substituents as each other. In compound group 2 of 5<img file="TW200529483A_D0070.tif" />Among the derivatives, in the fifth place except the 5 and 14 positions<img file="TW200529483A_D0071.tif" />One or more ring positions on the derivative may be substituted, but it is preferred that it is unsubstituted, that is, it is occupied by hydrogen.

<b>Compound group 3</b>

Compound group 3 is represented by chemical formula 3:<chemistry general="n"><img file="TW200529483A_D0072.tif" /></chemistry>

In compound group 3 of 5<img file="TW200529483A_D0073.tif" />Among the derivatives, R₂, R₃, R₉And R₁₀Each is the same or different, and each includes C which is substituted as necessary₁-C₄₀Carbon group or hydrocarbon group. R₂, R₃, R₉And R₁₀Group includes optionally substituted C₁-C₁₀A carbon group or a hydrocarbon group (especially an alkyl group), such as methyl, ethyl, propyl, butyl, pentyl, etc., is more preferable. In the fifth position except 2, 3, 9 and 10<img file="TW200529483A_D0074.tif" />One or more ring positions on can be substituted, but it is preferred that they are unsubstituted, that is, they are occupied by hydrogen. However, R₂And R₃Are preferably the same substituents as each other, and R₉And R₁₀The substituents which are the same as each other are preferred. R₂, R₃, R₉And R₁₀It's best if it's the same as each other.

Examples of compound group 3 are as follows:<chemistry general="n"><img file="TW200529483A_D0075.tif" /></chemistry>

<b>Compound group 4</b>

Compound group 4 is represented by chemical formula 4:<chemistry general="n"><img file="TW200529483A_D0076.tif" /></chemistry>

In compound group 4 of 5<img file="TW200529483A_D0077.tif" />Among the derivatives, R₂And R₃Each is the same or different, however, R₂And R₃The substituents which are the same as each other are preferred. R₂And R₃Group includes optionally substituted C₁-C₄₀A carbon group or a hydrocarbon group or a halogen group is preferred. In compound group 4 of 5<img file="TW200529483A_D0078.tif" />Among the derivatives, in the fifth position except the 2 and 3 positions<img file="TW200529483A_D0079.tif" />One or more of the ring positions may be substituted, but it is preferred that they are unsubstituted, that is, they are occupied by hydrogen.

An example of compound group 4 is as follows:<chemistry general="n"><img file="TW200529483A_D0080.tif" /></chemistry>

<b>Compound group 5</b>

Compound group 5 is represented by chemical formula 5:<chemistry general="n"><img file="TW200529483A_D0081.tif" /></chemistry>

In compound group 5 of 5<img file="TW200529483A_D0082.tif" />Among the derivatives, R₂, R₃, R₁₁And R₁₂Each is the same or different. However, R₂And R₃Are preferably the same substituents as each other, and R₁₁And R₁₂The substituents which are the same as each other are preferred. R₂, R₃, R₁₁And R₁₂All are preferably the same substituents as each other. R₂, R₃, R₁₁And R₁₂Group includes optionally substituted C₁-C₄₀A carbon group or a hydrocarbon group is preferable. R₂, R₃, R₁₁And R₁₂Group includes optionally substituted C₁-C₁₀Carbon group or hydrocarbon group, such as methyl, ethyl, propyl, butyl, pentyl, etc. are more preferable. In compound group 5 of 5<img file="TW200529483A_D0083.tif" />Among the derivatives, in the fifth position except 2, 3, 11 and 12<img file="TW200529483A_D0084.tif" />One or more ring positions on the derivative may be substituted, but it is preferred that it is unsubstituted, that is, it is occupied by hydrogen. Examples of compound group 5 are as follows:<chemistry general="n"><img file="TW200529483A_D0085.tif" /></chemistry>

<b>Compound group 6</b>

Compound group 6 is represented by chemical formula 6:<chemistry general="n"><img file="TW200529483A_D0086.tif" /></chemistry>

In compound group 6 of 5<img file="TW200529483A_D0087.tif" />Among the derivatives, R₂And R₉Each is the same or different. However, R₂And R₃The substituents which are the same as each other are preferred. R₂And R₉Group includes optionally substituted C₁-C₄₀A carbon group or a hydrocarbon group is preferable. In compound group 6 of 5<img file="TW200529483A_D0088.tif" />Among the derivatives, in the fifth position except the 2 and 9 positions<img file="TW200529483A_D0089.tif" />One or more of the ring positions may be substituted, but it is preferred that they are unsubstituted, that is, they are occupied by hydrogen.

An example of compound group 6 is as follows:<chemistry general="n"><img file="TW200529483A_D0090.tif" /></chemistry>

<b>Compound group 7</b>

Compound group 7 is represented by chemical formula 7:<chemistry general="n"><img file="TW200529483A_D0091.tif" /></chemistry>

In compound group 7 of 5<img file="TW200529483A_D0092.tif" />Among the derivatives, R₅, R₇, R₁₂And R₁₄Each is the same or different. However, R₅And R₁₄Are the same substituents as each other, and R₇And R₁₂The substituents which are the same as each other are preferred. R₅, R₁₄, R₇And R₁₂It is more preferable that the substituents are the same as each other. R₅, R₁₄, R₇And R₁₂Group includes optionally substituted C₁-C₄₀A carbon group or a hydrocarbon group is preferable. In compound group 7 of 5<img file="TW200529483A_D0093.tif" />Among the derivatives, in the fifth position except for positions 5, 14, 7 and 12<img file="TW200529483A_D0094.tif" />One or more of the ring positions may be substituted, but it is preferred that they are unsubstituted, that is, they are occupied by hydrogen.

An example of compound group 7 is as follows:<chemistry general="n"><img file="TW200529483A_D0095.tif" /></chemistry>

<b>Compound group 8</b>

Compound group 8 is represented by chemical formula 8:<chemistry general="n"><img file="TW200529483A_D0096.tif" /></chemistry>

In compound group 8 of 5<img file="TW200529483A_D0097.tif" />Derivatives and isomers, R₁, R₂, R₃, R₄, R₈, R₉, R₁₀, R₁₁, R₁₅, R₁₆And R₁₇Each is the same or different. R₁, R₂, R₃, R₄, R₈, R₉, R₁₀And R₁₁Each includes H, and replaces C as needed_1-40Carbon group or hydrocarbyl group, such as optionally substituted alkenyl group, alkaryl group, aryl group, etc., or halogen group such as F, Cl, Br. R₁, R₂, R₃, R₄, R₈, R₉, R₁₀And R₁₇Including C which is replaced as necessary_1-10Alkyl, for example, methyl, ethyl, propyl, butyl, pentyl, etc. is more preferred, methyl is the best; halogen, such as F, Cl, Br, F is the best; or R₂And R₃And R₉And R₁₀Together with the carbon atom to which it is connected, it forms via one or more oxygen or sulfur atoms or in the formula -N(R_a) (Where R_aC₄-C₄₀Saturated or unsaturated ring, optionally substituted C₄-C₁₀Saturated or unsaturated rings are more preferable. In chemical formula 8 of 5<img file="TW200529483A_D0098.tif" />Among the derivatives, R₁₅, R₁₆And R₁₇Each can be the same or different, R₁₅, R₁₆And R₁₇Are the same and preferably include the following groups: optionally substituted C₁-C₄₀Carbon group or hydrocarbon group, such as C₁-C₄₀Alkyl (in C₁-C₄Alkyl is preferred, and methyl, ethyl, n-propyl or isopropyl is most preferred), which can be substituted by, for example, halogen atoms as necessary; C₆-C₄₀Aryl (preferably phenyl), which can be substituted by, for example, halogen atoms as needed; C₆-C₄₀Aralkyl, which may be substituted by, for example, halogen atoms as necessary; C₁-C₄₀An alkoxy group, which may be substituted by, for example, a halogen atom as necessary; or C₆-C₄₀Aralkyloxy, which may be substituted by, for example, a halogen atom as necessary; or R₁₅And R₁₆Or R₁₆And R₁₇With, for example, the atom to which it is connected together form one or more oxygen or sulfur atoms or in the formula -N(R_a) (Where R_aC₄-C₄₀Saturated or unsaturated ring, optionally substituted C₄-C₁₀Saturated or unsaturated rings and/or isomers thereof are more preferable. R₁₅, R₁₆And R₁₇Each line is selected from C which is replaced as necessary_1-10Alkyl (C_1-4Better, and C_1-3Alkyl (e.g. isopropyl) is better) and optionally substituted C_6-10Aryl (preferably phenyl) is preferred.

In chemical formula 8 of 5<img file="TW200529483A_D0099.tif" />Among the derivatives, X is preferably silicon or germanium, and silicon is the most preferred.

In a preferred embodiment, when X is a silyl-forming silicon, R₁₅, R₁₆And R₁₇Groups which are the same as each other are preferred, for example, the same optionally substituted alkyl group, such as in triisopropylsilyl group. In this specific embodiment, R₁₅, R₁₆And R₁₇The same group is optionally substituted C_1-10(C_1-4Better, and C_1-3Still more preferred) An alkyl group is preferred. One of the preferred alkyl groups in this case is isopropyl.

The chemical formula-Si(R₁₅)(R₁₆)(R₁₇) Of the silyl group C₁-C₄₀Preferred optional substituents such as carbon group or hydrocarbyl group.

In addition, as an extension of this more preferred embodiment, when R₂, R₃, R₉And R₁₀Is C_1-10When alkyl, R₂, R₃, R₉And R₁₀One or more of them are preferably methyl, or R₁, R₂, R₃, R₄, R₈, R₉, R₁₀And R₁₁One or more of them are preferably F. In one of the more preferred embodiments of compound group 8, R₁, R₂, R₃, R₄, R₈, R₉, R₁₀And R₁₁Each is H. R₁₅, R₁₆And R₁₇Is C_1-10Alkyl, C_1-5The alkyl group is more preferably, for example, methyl, ethyl or propyl.

In another specific embodiment of group 8, the position in the<img file="TW200529483A_D0100.tif" />Any two or more substituents in the adjacent ring positions can be combined with the adjacent ring positions to which they are connected to form a further fusion as required.<img file="TW200529483A_D0101.tif" />The aromatic ring or heterocyclic ring system of the compound. Group of this type 85<img file="TW200529483A_D0102.tif" />An example of the compound is illustrated in the following group 8, example 6, where each pair of adjacent substituents R₁And R₂, R₃And R₄, R₈And R₉, And R₁₀And R₁₁Composition fused to five<img file="TW200529483A_D0103.tif" />The benzene ring.

In compound group 8 of 5<img file="TW200529483A_D0104.tif" />Among the derivatives, in five positions except 1, 2, 3, 4, 6, 8, 9, 10, 11 and 13<img file="TW200529483A_D0105.tif" />One or more ring positions on the derivative may be substituted, but it is preferred that it is unsubstituted, that is, it is occupied by hydrogen.

Examples of compounds of compound group 8 are as follows, where R₁₅, R₁₆And R₁₇And n and m are as previously explained above:<chemistry general="n"><img file="TW200529483A_D0106.tif" /></chemistry><chemistry general="n"><img file="TW200529483A_D0107.tif" /></chemistry>

<b>Compound group 9</b>

Compound group 9 is represented by chemical formula 9:<chemistry general="n"><img file="TW200529483A_D0108.tif" /></chemistry>

In compound group 9 of 5<img file="TW200529483A_D0109.tif" />Among the derivatives, R₂, R₃, R₇, R₈, R₁₅, R₁₆And R₁₇Each is the same or different, and each includes H, or C replaced as necessary₁-C₄₀Carbon group or hydrocarbon group. R₂And R₃They may be the same or different, but they are preferably the same substituents as each other. R₇And R₈They may be the same or different, but they are preferably the same substituents as each other. R₂, R₃, R₇And R₈The substituents which are the same as each other are preferred. R₂And R₃And R₇And R₈Together with the carbon atom to which it is connected, it forms via one or more oxygen or sulfur atoms or in the formula -N(R_a) (Where R_aC₄-C₄₀Saturated or unsaturated ring, C₄-C₁₀Saturated or unsaturated rings are better, thus forming a false five<img file="TW200529483A_D0110.tif" />The compound is the best. The better false five of compound group 9<img file="TW200529483A_D0111.tif" />Derivatives are shown in chemical formula 9a and chemical formula 9b and their isomers, most of which<img file="TW200529483A_D0112.tif" />One or more carbon atoms of the structure can be selected from N, P, As, O, S, Se, and Te, and substituted with N or S preferably heteroatoms.

<chemistry general="n"><img file="TW200529483A_D0113.tif" /></chemistry><chemistry general="n"><img file="TW200529483A_D0114.tif" /></chemistry>

In the false five of compound group 9 as exemplified in chemical formula 9a<img file="TW200529483A_D0115.tif" />Among the derivatives, R₁₉And R₂₀Are the same substituents, and include optionally substituted C_1-40A carbon group or a hydrocarbon group is preferable. R₁₉And R₂₀Each includes C which is substituted as needed and unsaturated as needed_1-40Carbon group or hydrocarbon group, for example, optionally substituted alkyl, alkenyl, alkynyl, aryl or aralkyl group, or R₁₉And R₂₀Together with the carbon atom to which it is attached or independently combined with the substituents on the appropriate adjacent atoms to form optionally via one or more oxygen or sulfur atoms or with the formula -N(R_a) (Where R_aIs a hydrogen atom or a hydrocarbyl group) inserted into the group indicated by the optionally substituted C₄-C₄₀Saturated or unsaturated rings are more preferable. (By R₁₉And R₂₀The ring formed with the carbon atom to which it is attached is preferably inserted via one or more oxygen atoms. However, R₁₉And R₂₀Are the same substituents and include hydrogen or saturated or unsaturated C_1-4Alkyl group, for example, methyl, ethyl, propyl, or butyl is best, R₁₉And R₂₀Each is preferably a methyl group or a hydrogen atom.

False five in compound groups 9a and 9b<img file="TW200529483A_D0116.tif" />Among the derivatives, R₁₅, R₁₆, R₁₇Can be the same or different, R₁₅, R₁₆And R₁₇It is the same and is the best as explained for the compound of Chemical Formula 8 above.

False five in compound group 9<img file="TW200529483A_D0117.tif" />In the derivative, one or more ring positions on the compound can be substituted, for example, to form an additional optionally substituted ring, but other ring positions are preferably unsubstituted, that is, they are occupied by hydrogen.

In the present invention<img file="TW200529483A_D0118.tif" />(Especially compound group 1-9), C₁-C₄₀The carbon group or the hydrocarbon group may be a saturated or unsaturated acyclic group, or a saturated or unsaturated cyclic group. Unsaturated acyclic or cyclic groups are preferred, especially alkenyl and alkynyl groups (especially ethynyl groups). When C₁-C₄₀When the carbon group or the hydrocarbon group is acyclic, the group may be straight or branched. C₁-C₄₀Carbon or hydrocarbon groups include, for example: C₁-C₄₀Alkyl, C₂-C₄₀Alkenyl, C₂-C₄₀Alkynyl, C₃-C₄₀Allyl, C₄-C₄₀Alkadienyl, C₄-C₄₀Polyalkenyl, C₆-C₁₆Aryl, C₆-C₄₀Alkylaryl, C₆-C₄₀Aralkyl, C₄-C₄₀Cycloalkyl, C₄-C₄₀Cycloalkenyl and so on. The preferred ones of the aforementioned groups are respectively C₁-C₂₀Alkyl, C₂-C₂₀Alkenyl, C₂-C₂₀Alkynyl, C₃-C₂₀Allyl, C₄-C₂₀Alkadienyl, C₆-C₁₂Aryl and C₄-C₂₀Polyalkenyl; better C₁-C₁₀Alkyl, C₂-C₁₀Alkenyl, C₂-C₁₀Alkynyl (especially ethynyl), C₃-C₁₀Allyl, C₄-C₁₀Alkadienyl, C₆-C₁₂Aryl and C₄-C₁₀Polyalkenyl; and the best is C_2-10Alkynyl.

Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, n-butyl, tert-butyl, dodecyl, trifluoromethyl, perfluoro-n-butyl, 2,2,2- Trifluoroethyl, benzyl, 2-phenoxyethyl, etc. Examples of alkynyl groups are ethynyl and propynyl. Examples of aryl groups are, but are not limited to, phenyl, 2-tolyl, 3-tolyl, 4-tolyl, naphthyl, biphenyl, 4-phenoxyphenyl, 4-fluorophenyl, 3- Methoxycarbonylphenyl, 4-methoxycarbonylphenyl and the like. Examples of alkoxy groups are, but are not limited to, methoxy, ethoxy, 2-methoxyethoxy, tert-butoxy and the like. Examples of aryloxy groups are, but are not limited to, phenoxy, naphthyloxy, phenylphenoxy, 4-tolyloxy and the like. Examples of amine groups include, but are not limited to, dimethylamino, methylamino, toluino, anilino, and the like.

In the present invention<img file="TW200529483A_D0119.tif" />In R₁Wait for C₁-C₄₀The optional substituents on the carbon group or the hydrocarbon group are preferably selected from the following groups: silyl group, sulfonic acid group, sulfonyl group, methionyl group, amine group, imino group, nitrogen group, mercapto group, cyano group , Nitro, halo, C_1-4Alkyl, C_6-12Aryl, C_1-4Alkoxy, hydroxyl, and/or all chemically possible combinations thereof. The more preferred of these non-essential substituents are silyl and C_6-12The aryl group, and the best is the silyl group.

The silyl group that can be substituted as needed in this specification can have the chemical formula: -Si(R₁₅)(R₁₆)(R₁₇) Display, where R₁₅, R₁₆And R₁₇Each can be the same or different, and each represents hydrogen, which can be replaced by, for example, a halogen atom as needed.₁-C₄₀Alkyl (in C₁-C₄Alkyl is preferred, and methyl, ethyl, n-propyl or isopropyl is the best); if necessary, it can be substituted by, for example, a halogen atom.₆-C₄₀Aryl (preferably phenyl); C which can be substituted by, for example, halogen atoms as required₆-C₄₀Aralkyl; C which can be substituted by, for example, halogen atoms as required₁-C₄₀Alkoxy; or C which can be substituted by, for example, halogen atoms as needed₆-C₄₀Aralkyloxy. R₁₅, R₁₆And R₁₇Each is selected from C which is substituted as necessary_1-10Alkyl (C_1-4Better, and C_1-3Alkyl is better, such as isopropyl) and optionally substituted C_6-10Aryl (preferably phenyl) is preferred.

In a preferred embodiment of the silyl group, R₁₅, R₁₆And R₁₇Groups which are the same as each other are preferred, for example, the same optionally substituted alkyl group, such as in triisopropylsilyl group. In this preferred embodiment, R₁₅, R₁₆And R₁₇The same group is optionally substituted C_1-10(C_1-4Better, and C_1-3Still more preferred) An alkyl group is preferred. The preferred alkyl group in this case is isopropyl.

The chemical formula-Si(R₁₅)(R₁₆)(R₁₇) Of the silyl group C₁-C₄₀Preferred optional substituents such as carbon group or hydrocarbyl group.

Silyl-Si(R₁₅)(R₁₆)(R₁₇) Examples are, but not limited to, trimethylsilyl, triethylsilyl, tripropylsilyl, dimethylethylsilyl, diethylmethylsilyl, dimethylsilyl Propylpropylsilyl, dimethylisopropylsilyl, dipropylmethylsilyl, diisopropylmethylsilyl, dipropylethylsilyl, diisopropylethyl Diethylsilyl, diethylisopropylsilyl, triisopropylsilyl, trimethoxysilyl, triethoxysilyl, triphenylsilyl, diphenylisopropyl Silyl, diisopropylphenylsilyl, diphenylethylsilyl, diethylphenylsilyl, diphenylmethylsilyl, triphenoxysilyl, Dimethylmethoxysilyl, dimethylphenoxysilyl, methylmethoxyphenyl, etc. For each example listed above, the alkyl group, aryl group or alkoxy group may be substituted as necessary.

According to the fifth of the present invention<img file="TW200529483A_D0120.tif" />The compounds are the best compounds of compound groups 1, 2, 8, and 9, and compound groups 1 and 8 are particularly preferable. Examples of compounds of groups 1 and 2 include, but are not limited to: 6,13-bis(trimethylsilylethynyl)penta<img file="TW200529483A_D0121.tif" />, 6,13-bis(triethylsilylethynyl) five<img file="TW200529483A_D0122.tif" />, 6,13-bis(tripropylsilylethynyl) five<img file="TW200529483A_D0123.tif" />, 6,13-bis(dimethylethylsilylethynyl) five<img file="TW200529483A_D0124.tif" />, 6,13-bis(diethylmethylsilylethynyl) five<img file="TW200529483A_D0125.tif" />, 6,13-bis(dimethylpropylsilylethynyl) five<img file="TW200529483A_D0126.tif" />, 6,13-bis(dimethylisopropylsilylethynyl) five<img file="TW200529483A_D0127.tif" />, 6,13-bis(dipropylmethylsilylethynyl) five<img file="TW200529483A_D0128.tif" />, 6,13-bis(diisopropylmethylsilylethynyl) five<img file="TW200529483A_D0129.tif" />, 6,13-bis(dipropylethylsilylethynyl) five<img file="TW200529483A_D0130.tif" />, 6,13-bis(diisopropylethylsilylethynyl) five<img file="TW200529483A_D0131.tif" />, 6,13-bis(diethylisopropylsilylethynyl) five<img file="TW200529483A_D0132.tif" />, 6,13-bis(triisopropylsilylethynyl) five<img file="TW200529483A_D0133.tif" />, 6,13-bis(trimethoxysilylethynyl) five<img file="TW200529483A_D0134.tif" />, 6,13-bis(triethoxysilylethynyl) five<img file="TW200529483A_D0135.tif" />, 6,13-bis(triphenylsilylethynyl) five<img file="TW200529483A_D0136.tif" />, 6,13-bis(diphenylisopropylsilylethynyl) five<img file="TW200529483A_D0137.tif" />, 6,13-bis(diisopropylphenylsilylethynyl) five<img file="TW200529483A_D0138.tif" />, 6,13-bis(diphenylethylsilylethynyl) five<img file="TW200529483A_D0139.tif" />, 6,13-bis(diethylphenylsilylethynyl) five<img file="TW200529483A_D0140.tif" />, 6,13-bis(diphenylmethylsilylethynyl) five<img file="TW200529483A_D0141.tif" />, 6,13-bis(triphenoxysilylethynyl) five<img file="TW200529483A_D0142.tif" />, 6,13-bis(dimethylmethoxysilylethynyl) five<img file="TW200529483A_D0143.tif" />, 6,13-bis(dimethylphenoxysilylethynyl) five<img file="TW200529483A_D0144.tif" />, 6,13-bis(methylmethoxyphenylethynyl) five<img file="TW200529483A_D0145.tif" />, 6,13-bis(cyclopentamethylene silane) five<img file="TW200529483A_D0146.tif" />, 6,13-bis(cyclotetramethylenesilane) five<img file="TW200529483A_D0147.tif" />, 5,14-bis(trimethylsilylethynyl) five<img file="TW200529483A_D0148.tif" />, 5,14-bis(triethylsilylethynyl) five<img file="TW200529483A_D0149.tif" />, 5,14-bis(tripropylsilylethynyl) five<img file="TW200529483A_D0150.tif" />, 5,14-bis(dimethylethylsilylethynyl) five<img file="TW200529483A_D0151.tif" />, 5,14-bis(diethylmethylsilylethynyl) five<img file="TW200529483A_D0152.tif" />, 5,14-bis(dimethylpropylsilylethynyl) five<img file="TW200529483A_D0153.tif" />, 5,14-bis(dimethylisopropylsilylethynyl) five<img file="TW200529483A_D0154.tif" />, 5,14-bis(dipropylmethylsilylethynyl) five<img file="TW200529483A_D0155.tif" />, 5,14-bis(diisopropylmethylsilylethynyl) five<img file="TW200529483A_D0156.tif" />, 5,14-bis(dipropylethylsilylethynyl) five<img file="TW200529483A_D0157.tif" />, 5,14-bis(diisopropylethylsilylethynyl) five<img file="TW200529483A_D0158.tif" />, 5,14-bis(diethylisopropylsilylethynyl) five<img file="TW200529483A_D0159.tif" />, 5,14-bis(triisopropylsilylethynyl) five<img file="TW200529483A_D0160.tif" />, 5,14-bis(trimethoxysilylethynyl) five<img file="TW200529483A_D0161.tif" />, 5,14-bis(triethoxysilylethynyl) five<img file="TW200529483A_D0162.tif" />, 5,14-bis(triphenylsilylethynyl) five<img file="TW200529483A_D0163.tif" />, 5,14-bis(diphenylisopropylsilylethynyl) five<img file="TW200529483A_D0164.tif" />, 5,14-bis(diisopropylphenylsilylethynyl) five<img file="TW200529483A_D0165.tif" />, 5,14-bis(diphenylethylsilylethynyl) five<img file="TW200529483A_D0166.tif" />, 5,14-bis(diethylphenylsilylethynyl) five<img file="TW200529483A_D0167.tif" />, 5,14-bis(diphenylmethylsilylethynyl) five<img file="TW200529483A_D0168.tif" />, 5,14-bis(triphenoxysilylethynyl) five<img file="TW200529483A_D0169.tif" />, 5,14-bis(dimethylmethoxysilylethynyl) five<img file="TW200529483A_D0170.tif" />, 5,14-bis(dimethylphenoxysilylethynyl) five<img file="TW200529483A_D0171.tif" />, 5,14-bis(methylmethoxyphenylethynyl) five<img file="TW200529483A_D0172.tif" />。

Examples of compounds of groups 8 and 9 include, but are not limited to: 2,3,9,10-tetramethyl-6,13-bis(triisopropylsilylethynyl)penta<img file="TW200529483A_D0173.tif" />, 5,11-bis(triisopropylsilylethynyl)anthra[2,3-<i>b</i>：6,7-<i>b'</i>]Dithiophene, 5,11-bis(triisopropylsilylethynyl)anthra[2,3-<i>b</i>：7,6-<i>b'</i>]Dithiophene, 1,8-difluoro-6,13-bis(triisopropylsilylethynyl)penta<img file="TW200529483A_D0174.tif" />, 1,11-difluoro-6,13-bis(triisopropylsilylethynyl) five<img file="TW200529483A_D0175.tif" />And 2,3,9,10-tetrafluoro-6,13-bis(triisopropylsilylethynyl) penta<img file="TW200529483A_D0176.tif" />。

The preferable ones of the compound groups 1 and 8 are the compounds of chemical formula 1A, 8A or 8B, especially the chemical formula 1A:<chemistry general="n"><img file="TW200529483A_D0177.tif" /></chemistry><chemistry general="n"><img file="TW200529483A_D0178.tif" /></chemistry><chemistry general="n"><img file="TW200529483A_D0179.tif" /></chemistry>Where each R'is selected from C_2-40Alkyl, C_2-40Alkoxy, C_2-40Alkenyl, C_2-40Alkynyl, C_6-16Aryl or heteroaryl, C_6-40Aryloxy, C₇-C₄₀Alkyl aryloxy, C₂-C₄₀Alkoxycarbonyl, C₇-C₄₀Aryloxycarbonyl, or silyl group, each of which may be substituted if necessary, or cyano (-CN), carbamate (-C(=O)NH₂), haloformyl (-C(=O)-X, where X represents a halogen atom), formyl (-C(=O)-H), isocyanate, isocyanate, thiocyanate or Thioisocyanate group, optionally substituted amine group, imino group, hydroxyl group, halo group, sulfonic acid group, sulfonyl group, mercapto group, or nitro group; and m and n in chemical formula 8B are each 0, 1, 2, 3, or 4, 0, 1 or 2 is more preferable. In the chemical formulas 1A, 8A and 8B, each R'is selected from C_6-18The aryl group and the silyl group can be preferably substituted as needed. In the chemical formulas 1A, 8A and 8B, at least one R'(and two R'is best) is preferably a silyl group, wherein the silyl group is preferably as defined above, that is, the chemical formula -Si(R₁₅)(R₁₆)(R₁₇) Of the silyl group. Therefore, these latter very good compounds have chemical formulas 1A', 8A' and 8B':<chemistry general="n"><img file="TW200529483A_D0180.tif" /></chemistry><chemistry general="n"><img file="TW200529483A_D0181.tif" /></chemistry><chemistry general="n"><img file="TW200529483A_D0182.tif" /></chemistry>

In one type of preferred embodiment, the R in the chemical formulas 1A', 8A' and 8B'₁₅, R₁₆And R₁₇It is preferably the same as each other, for example, the same alkyl group, such as 6,13-bis(triisopropylsilylethynyl)penta<img file="TW200529483A_D0183.tif" />middle. In this particularly preferred embodiment, R₁₅, R₁₆And R₁₇Department of the same C_1-10(C_1-4Better and C_1-3More preferably) An alkyl group is preferred, and it may be substituted if necessary. The optionally substituted isopropyl group is one of the preferred alkyl groups in this embodiment.

In some cases, you may wish to control more<img file="TW200529483A_D0184.tif" />Solubility in common organic solvents to make the device easier to manufacture. This may be advantageous for manufacturing, for example, FETs, in which, for example, a dielectric solution is applied to many<img file="TW200529483A_D0185.tif" />There are so many layers<img file="TW200529483A_D0186.tif" />The tendency to dissolve. In addition, once the element is formed, it is much less insoluble<img file="TW200529483A_D0187.tif" />May have less tendency to "bleed" through the organic layer. In controlling the above chemical formula 1B-5<img file="TW200529483A_D0188.tif" />In a specific example of the solubility of the derivative, R₁₅, R₁₆And R₁₇At least one of them contains optionally substituted aryl (preferably phenyl). Therefore, R₁₅, R₁₆And R₁₇At least one of C can be substituted as necessary_6-18Aryl (preferably phenyl), optionally substituted C_6-18Aryloxy (preferably phenoxy), optionally substituted C_6-20Aralkyl (e.g. benzyl), or optionally substituted C_6-20Aralkyloxy (e.g. benzyloxy). In this case, if it is in R₁₅, R₁₆And R₁₇The remaining groups in C are optionally substituted C_1-10(C_1-4More preferably) alkyl is preferred. An example of this specific embodiment is shown in the following chemical formula 1C, where Ar represents an aryl group-containing group, for example, optionally substituted C_6-18Aryl, optionally substituted C_6-18Aryloxy, optionally substituted C_6-20Aralkyl or optionally substituted C_6-20Aralkyloxy:<chemistry general="n"><img file="TW200529483A_D0189.tif" /></chemistry>

In the chemical formula 1C, R₁₅And R₁₇The same groups as each other are preferred, for example, isopropyl.

Examples of compounds of formula 1C include, but are not limited to, 6,13-bis(triphenylsilylethynyl)penta<img file="TW200529483A_D0190.tif" />, 6,13-bis(diphenylisopropylsilylethynyl) five<img file="TW200529483A_D0191.tif" />, 6,13-bis(diisopropylphenylsilylethynyl) five<img file="TW200529483A_D0192.tif" />, 6,13-bis(diphenylethylsilylethynyl) five<img file="TW200529483A_D0193.tif" />, 6,13-bis(diethylphenylsilylethynyl) five<img file="TW200529483A_D0194.tif" />, 6,13-bis(diphenylmethylsilylethynyl) five<img file="TW200529483A_D0195.tif" />, 6,13-bis(triphenoxysilylethynyl) five<img file="TW200529483A_D0196.tif" />, 6,13-bis(dimethylphenoxysilylethynyl) five<img file="TW200529483A_D0197.tif" />, 6,13-bis(methylmethoxyphenylethynyl) five<img file="TW200529483A_D0198.tif" />, 5,14-bis(triphenylsilylethynyl) five<img file="TW200529483A_D0199.tif" />, 5,14-bis(diphenylisopropylsilylethynyl) five<img file="TW200529483A_D0200.tif" />, 5,14-bis(diisopropylphenylsilylethynyl) five<img file="TW200529483A_D0201.tif" />, 5,14-bis(diphenylethylsilylethynyl) five<img file="TW200529483A_D0202.tif" />, 5,14-bis(diethylphenylsilylethynyl) five<img file="TW200529483A_D0203.tif" />, 5,14-bis(diphenylmethylsilylethynyl) five<img file="TW200529483A_D0204.tif" />, 5,14-bis(triphenoxysilylethynyl) five<img file="TW200529483A_D0205.tif" />, 5,14-bis(dimethylphenoxysilylethynyl) five<img file="TW200529483A_D0206.tif" />, 5,14-bis(methylmethoxyphenylethynyl) five<img file="TW200529483A_D0207.tif" />。

Additional examples of preferred compounds of groups 1 and 8 are as previously described under the general description of each group.

In a preferred embodiment of the present invention, the semiconductivity is more<img file="TW200529483A_D0208.tif" />Has more than 10^-5The field effect rate of movement μ in square centimeters/volt/second is greater than 10^-4Cm²/volt/second is better, more than 10^-3Cm²/volt/second is better, more than 10^-2Square centimeter/volt/second is better and more than 10^-1The square centimeter/volt/second is best.

The adhesive (which is a polymer, which may include an insulating adhesive or a semiconducting adhesive or a mixture thereof) can be referred to as an organic adhesive, a polymeric adhesive, or simply an adhesive in the text.

The preferred adhesive according to the present invention is a material with a low permittivity, that is, a permittivity of 3.3 or less at 1,000 Hz<img file="TW200529483A_D0209.tif" />s material. The organic binder preferably has a permittivity of less than 3.0 at 1,000 Hz, and more preferably 2.9 or less. The organic binder preferably has a permittivity greater than 1.7 at 1,000 Hz. The permittivity of the adhesive is particularly preferably in the range from 2.0 to 2.9. Although not wishing to be bound by any particular theory, it is believed that the use of an adhesive with a permittivity greater than 3.3 at 1,000 Hz can result in a decrease in the mobility of the OSC layer in electronic components (such as OFETs). In addition, the high permittivity adhesive will also cause the increased current hysteresis of the device, which is undesirable.

An example of a suitable organic binder is polystyrene. Further examples are described below.

In one type of preferred embodiment, the organic binder has at least 95% of the atoms, 98% is more preferred, and all of them are particularly preferred. The organic binder is a binder composed of hydrogen, fluorine, and carbon atoms.

The binder generally contains conjugated bonds, especially conjugated double bonds and/or aromatic rings.

The adhesive should be able to form a film, preferably a flexible film. Polymers of styrene and α-methylstyrene can be suitably used, such as copolymers of styrene, α-methylstyrene, and butadiene.

The low-permittivity adhesive used in the present invention has very few permanent dipoles, otherwise it will cause random fluctuations in molecular energy. The permittivity (dielectric constant) can be measured using the ASTM D150 test method.

In the present invention, it is also preferable to use a binder with low polarity and solubility parameters contributed by hydrogen bonding as this type of material with low permanent dipole. A preferred range of the solubility parameter of the adhesive used according to the present invention is provided in Table 1 below.

<tables><img file="TW200529483A_D0210.tif" /></tables>

The three-dimensional solubility parameters listed above include: dispersion (δ_d), polarity (δ_p) And hydrogen bonding (δ_h) Ingredients (CM Hansen, Ind. Eng. and Chem., Prod. Res. and Devl., 9, No 3, p282, 1970). These parameters can be determined experimentally or calculated from the known contribution of the molar group, as described in the Handbook of Solubility Parameters and Other Cohesion Parameters (Handbook of Solubility Parameters and Other Cohesion Parameters), edited by AFM Barton, CRC Press, 1991. The solubility parameters of many known polymers are also listed in this publication.

It is hoped that the permittivity of the adhesive has very little frequency dependence. This is typical of non-polar materials. The polymer and/or copolymer can be selected as the binder according to the permittivity of its substituents. Table 2 shows a list of low-polarity adhesives suitable for the present invention (but it is not limited to these examples):<tables><img file="TW200529483A_D0211.tif" /></tables>

Other polymers suitable as binders include: poly(1,3-butadiene) or polyphenylene. Copolymers containing recurring units of the above polymers are also suitable as binders. Copolymers provide improvements and more<img file="TW200529483A_D0212.tif" />The compatibility, the possibility to modify the morphology and/or glass transition temperature of the final layer composition. It should be understood that some of the materials in the above table are not soluble in the common solvents used to prepare the layer. In these cases, analogs can be used as copolymers. Some examples of copolymers are shown in Table 3 (but not limited to these examples). Random or block copolymers can be used. Some more polar monomer components can also be added, as long as the overall composition can maintain low polarity.

<tables><img file="TW200529483A_D0213.tif" /></tables>

Other copolymers may include: branched or unbranched polystyrene-block-polybutadiene, polystyrene-block (polyethylene-random-butene)-block-polystyrene, polystyrene Ethylene-block-polybutadiene-block-polystyrene, polystyrene-(ethylene-propylene)-diblock-copolymer (for example, KRATON®-G1701E, Shell), poly(propylene-co- Ethylene) and poly(styrene-co-methyl methacrylate).

The preferred insulating adhesives used in the organic semiconductor layer formulation according to the present invention are poly(α-methylstyrene), polyvinyl cinnamate, poly(4-vinylbiphenyl), poly(4-methylstyrene) Styrene), and Topas^TM 8007. However, the best insulating adhesives are poly(α-methylstyrene), polyvinyl cinnamate, and poly(4-vinyl biphenyl).

As mentioned above, the organic binder itself can be a semiconductor, which is referred to as a semiconducting binder in the text. It is still preferable that the semiconducting adhesive is an adhesive with a low permittivity as defined in the text. The semiconductive adhesive used in the present invention has a number average molecular weight of at least 1500-2000 (M_n) Preferably, at least 3000 is more preferable, at least 4000 is more preferably, and at least 5000 is best. Semiconductive adhesive has at least 10^-5The charge carrier mobility μ of cm²/volt/sec is better, at least 10^-4The square centimeter/volt/second is better.

A preferred type of semiconducting adhesive has the reproduction unit of chemical formula 10:<chemistry general="n"><img file="TW200529483A_D0214.tif" /></chemistry>

Where Ar¹, Ar²And Ar³It can be the same or different. When in different reproduction units, each represents an optionally substituted aryl group (monocyclic or polycyclic), and in the semiconductor adhesive, n is an integer of at least 6 and the ratio is at least 10. Better, at least 15 is more preferably and at least 20 is best. In Ar¹, Ar²And Ar³In this case, the monocyclic aryl group has only one aromatic ring, such as a phenyl group or a phenylene group. Polycyclic aryl groups have two or more aromatic rings, which can be condensed (such as naphthyl or naphthylene), individual covalent linkages (such as biphenyl), and/or condensed and individually linked aromatic rings. The combination of those. Each Ar¹, Ar²And Ar³An aryl group that is substantially conjugated to substantially the entire group is preferred.

A preferred type of semiconducting adhesive is an adhesive that contains substantially conjugated reproduction units. The semiconducting polymer can be a homopolymer or copolymer (including block copolymer) of the general formula 11: A_(c)B_(d)...X_(Z) Chemical formula 11

Wherein A, B,..., Z each represents a monomer unit, and (c), (d),..., (z) each represents the molar fraction of the respective monomer unit in the polymer, namely Each of (c), (d),..., (z) is a value from 0 to 1 and the sum of (c)+(d)+...+(z)=1. Examples of monomer units A, B, ..., Z include chemical formula 10 and the units of chemical formulas 12 to 17 shown below:<chemistry general="n"><img file="TW200529483A_D0215.tif" /></chemistry>

Wherein R1 and R2 can be respectively: H; optionally substituted alkyl; alkoxy; sulfanyl; acyl; optionally substituted aryl; fluorine atom; cyano; nitro; chemical formula -N( R_a)(R_b) Is optionally substituted second or third alkylamine or arylamine, wherein R_aAnd R_bEach can represent H, optionally substituted alkyl, aryl, optionally substituted aryl, alkoxy or polyalkoxy, or other substituents, and^＊Any end group or end-capping group, including hydrogen (alkyl and aryl groups can be fluorinated if necessary);<chemistry general="n"><img file="TW200529483A_D0216.tif" /></chemistry>Where X can be Se, Te, O, S or -N(R_c), X is O, S or -N(R_c)-Better, where R_cRepresents H, optionally substituted alkyl group or optionally substituted aryl group; and R1 and R2 are as previously described in chemical formula 12;<chemistry general="n"><img file="TW200529483A_D0217.tif" /></chemistry>Wherein R1, R2 and X are as previously described with respect to chemical formulas 12 and 13, respectively;<chemistry general="n"><img file="TW200529483A_D0218.tif" /></chemistry>Wherein R1, R2, and X are as previously described with respect to chemical formulas 12 and 13, respectively; and Z represents -C(T₁)=C(T₂)-, -CC-, -N(R')-, -N=N-, (R')=N-, -N=C(R')-, where T₁And T₂Each represents -H, Cl, F, -CN or lower alkyl, and R'represents -H, alkyl, substituted alkyl, aryl, or substituted aryl;<chemistry general="n"><img file="TW200529483A_D0219.tif" /></chemistry>Wherein R1 and R2 are as described in the previous chemical formula 12;<chemistry general="n"><img file="TW200529483A_D0220.tif" /></chemistry>Wherein R1 to R4 can be selected from the same listed groups as explained for R1 and R2 in Chemical Formula 12, respectively.

In the case of the polymerization formulas described in the text, such as formulas 10 to 17, the polymer can be end-capped with any end group, that is, any end-capping or leaving group, including hydrogen.

In the case of a block copolymer, each monomer A, B, ..., Z may be a conjugated oligomer or a polymer including, for example, 2 to 50 units of the chemical formula 12-17. The semiconducting binder preferably includes: aromatic amines, pyridines, thiophenes, spirobiphenes and/or optionally substituted aryl groups (for example, phenylene), arylamines are more preferred, and triarylamines are more preferred. The aforementioned groups may be linked via a further conjugated group (for example, vinylene). In addition, the semiconducting adhesives include polymers (homopolymers or copolymers, including block copolymers) containing one or more of the aforementioned aromatic amines, sulphur, thiophenes and/or optionally substituted aromatic groups. . A preferred semiconducting adhesive includes homopolymers or copolymers (including block copolymers) containing aromatic amines (preferably triarylamines) and/or tungsten units. Another preferred semiconducting adhesive includes homopolymers or copolymers (including block copolymers) containing thiophene and/or thiophene units.

The semiconductive adhesive may also contain: carbazole, stilbene reproduction unit. For example, polyvinylcarbazole or polystilbene polymers or copolymers can be used. The semiconductive adhesive may contain as many<img file="TW200529483A_D0221.tif" />Segment (for example, as described in the reproduction unit of formula A above), to improve and dissolve more<img file="TW200529483A_D0222.tif" />Compatibility of molecules.

The best semiconducting adhesive used in the organic semiconductor layer formulation according to the present invention is poly(9-vinylcarbazole) and PTAA1.

In order to apply the semiconducting layer to the p-channel FET, it is hoped that the semiconducting adhesive should have more<img file="TW200529483A_D0223.tif" />Semiconductors have high ionization potential, otherwise the adhesive will form hole traps. In n-channel materials, semiconducting adhesives should have a lower electron affinity than n-type semiconductors to avoid electron capture.

The formula according to the present invention can be prepared by a method including the following steps: (i) First<img file="TW200529483A_D0224.tif" />The compound is mixed with the organic binder, and this mixing includes mixing the two components together in a solvent or a solvent mixture. The solvent can be a single solvent, or multiple<img file="TW200529483A_D0225.tif" />The compound and the organic binder are each dissolved in a separate solvent, and then the two resulting solutions are mixed to mix the compound; and (ii) will contain multiple<img file="TW200529483A_D0226.tif" />The solvent of the compound and the organic binder is applied to the substrate; and (iii) the solvent is evaporated as necessary to form the layer of the present invention.

Adhesives can be<img file="TW200529483A_D0227.tif" />If necessary, in the presence of a solvent, mixed or dissolved in the binder precursor, such as liquid monomers, oligomers or cross-linkable polymers, and for example by dipping, spraying, lacquering or printing the mixture or solution It is deposited on a substrate to form a liquid layer, and then, for example, by exposure to radiation, heat or electron beams, the liquid monomer, oligomer or crosslinkable polymer is cured to produce a solid layer, which is formed in situ.

If a pre-formed adhesive is used, it can be combined with more<img file="TW200529483A_D0228.tif" />They are dissolved together in a suitable solvent, and the solution is deposited on the substrate to form a liquid layer, for example, by dipping, spraying, lacquering or printing, and then the solvent is removed to leave a solid layer. It should be understood that the selected solvent can dissolve the adhesive and multiple<img file="TW200529483A_D0229.tif" />, And when it evaporates from the solution blend, it produces a tight, flawless layer. Adhesive or more<img file="TW200529483A_D0230.tif" />The appropriate solvent can be determined by preparing a contour diagram of the material at the concentration of the mixture to be used as described in ASTM method D 3132. Add the materials to a wide variety of solvents as specified in the ASTM method.

It should also be understood that according to the present invention, the formulation may contain one or more<img file="TW200529483A_D0231.tif" />Compounds and/or one or more binders, and the preparation method of the formula can be applied to these formulas.

Examples of organic solvents that can be considered are: CH₂Cl₂, CHCl₃, Monochlorobenzene, o-dichlorobenzene, tetrahydrofuran, methoxybenzene, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1,4-dioxane, acetone, methyl ethyl ketone, 1,2-Dichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, ethyl acetate, n-butyl acetate, dimethylformamide, two Methyl acetamide, dimethyl sulfoxide, tetrahydronaphthalene, decalin and/or mixtures thereof. After proper mixing and aging, the solution is classified as one of the following: complete solution, boundary solution, or insoluble. Draw contours to draw the solubility parameter-hydrogen bonding limit that divides solubility and insolubility. The "complete" solvent that falls within the solubility region can be selected from literature values, such as those published in "Crowley, JD, Teague, GSJr and Lowe, JWJr., Journal of Paint Technology, 38, No. 496, 296 (1966)" . Solvent blends can also be used, and they can be identified as described in "Solvents, WHEllis, Federation of Societies for Coatings Technology, p9-10, 1986". This procedure can obtain the ability to simultaneously dissolve the adhesive and multiple<img file="TW200529483A_D0232.tif" />The blend of "non" solvents, although it is desirable to have at least one true solvent in the blend.

The preferred solvents used in the organic semiconducting layer formulation according to the present invention used in insulating and semiconducting adhesives and their mixtures are: xylene, toluene, tetralin and o-dichlorobenzene.

According to the formula of the present invention or the adhesive in the layer is more<img file="TW200529483A_D0233.tif" />The ratio is typically 20:1 to 1:20 (weight ratio), preferably 10:1 to 1:10, more preferably 5:1 to 1:5, more preferably 3:1 to 1:3, 2 :1 to 1:2 is even better and 1:1 is especially good. Surprisingly and beneficially found that there will be more<img file="TW200529483A_D0234.tif" />Dilution in the adhesive has little or no detrimental effect on the rate of charge mobility compared to that expected by the prior art.

According to the present invention, it is further discovered that the degree of solid content in the organic semiconducting layer formulation is also a factor in obtaining the improved mobility value of electronic components such as OFET. The solid content of the formula is generally expressed as follows:<maths><img file="TW200529483A_D0235.tif" /></maths>Among them: a=many<img file="TW200529483A_D0236.tif" />The quality, b=the quality of the adhesive and c=the quality of the solvent.

The solid content of the formula is preferably 0.1 to 10% by weight, more preferably 0.5 to 5% by weight.

Surprisingly and beneficially found that there will be more<img file="TW200529483A_D0237.tif" />Dilution in the adhesive has little or no effect on the rate of charge mobility compared to that expected by the prior art.

It is hoped to produce small structures in new microelectronic components to reduce cost (more components/unit area) and power consumption. The patterning of the layers of the present invention can be performed by lithography or electron beam lithography.

Liquid coating of organic electronic components such as field effect transistors is better than vacuum deposition technology. Many inventions<img file="TW200529483A_D0238.tif" />And the adhesive mixture can use many liquid coating techniques. The organic semiconductor layer can be added to the final device structure by, for example, but not limited to the following methods: dip coating, spin coating, inkjet printing, lithography, screen printing, squeegee coating, rotary printing, reverse roll printing, lithographic transfer Printing, offset printing, printing, spraying, brushing or pad printing. The invention is particularly suitable for spin-coating organic semiconductor layers into the final device structure.

The present invention has been selected<img file="TW200529483A_D0239.tif" />And the adhesive composition can be applied to the pre-manufactured device substrate through inkjet printing or micro-dispensing. Industrial piezoelectric printing heads, such as, but not limited to, those supplied by Aprion, Hitachi-Koki, InkJet Technology, On Target Technology, Picojet, Spectra, Trident, Xaar, can be used to apply organic semiconductor layers to substrates. good. In addition, semi-industrial heads, such as those manufactured by Brother, Epson, Konica, Seiko Instruments, Toshiba TEC, or single-nozzle micro-dispensers, such as those manufactured by Microdrop and Microfab, can be used.

In order to use inkjet printing or micro-distribution coating, it is necessary to<img file="TW200529483A_D0240.tif" />And the adhesive composition is dissolved in a suitable solvent. The solvent must meet the aforementioned requirements and must not have any adverse effects on the selected print head. In addition, the solvent should have a boiling point of &gt;100°C, preferably &gt;140°C and more preferably &gt;150°C, to prevent operability problems caused by the solution drying up in the print head. Suitable solvents include substituted and unsubstituted xylene derivatives, di-C_1-2Alkylformamide, substituted and unsubstituted methoxybenzene and other phenol-ether derivatives, substituted heterocycles such as substituted pyridine, pyridine<img file="TW200529483A_D0241.tif" />, Pyrimidine, pyrrolidone, substituted and unsubstituted<i>N,N</i>-Two-C_1-2Alkylanilines and other fluorinated or chlorinated aromatic compounds.

Used to deposit adhesives using inkjet printing/multi<img file="TW200529483A_D0242.tif" />Preferred solvents for the formulation include benzene derivatives, which have a benzene ring substituted with one or more substituents, in which the total number of carbon atoms in one or more substituents is at least three. For example, benzene derivatives can be substituted with monopropyl or trimethyl, in either case totaling at least three carbon atoms. This solvent can be formed to reduce or prevent ink jet clogging and component separation during the spraying process.<img file="TW200529483A_D0243.tif" />Inkjet fluid. The solvent may include a solvent selected from the following examples: dodecylbenzene; 1-methyl-4-tert-butylbenzene; terpene alcohol; 1,8-dienterpene, isoxane, 1,4(8)- Correct<img file="TW200529483A_D0244.tif" />Diene; o-isopropyl toluene; diethylbenzene. The solvent can be a mixture of solvents, that is, a combination of two or more solvents. Preferably, each solvent has a boiling point of &gt;100°C, more preferably &gt;140°C. Such solvents can also improve film formation in the deposited layer and reduce defects in the layer.

Inkjet fluids (i.e. solvents, adhesives and more<img file="TW200529483A_D0245.tif" />The mixture) has 1-100 mPa. Second (mPa.s) has a better viscosity at 20°C, 1-50 mPa.s. The second is better and 1-30 mPa. The second is the best.

The adhesive used in the present invention can also adjust the viscosity of the coating solution to meet the requirements of a specific printing head.

The semiconducting layer of the present invention is typically at most 1 micrometer (=1 μm) thick, although it can be thicker if necessary. The exact thickness of the layer will depend, for example, on the needs of the electronic components in which the layer is used. For use in OFETs or OLEDs, the layer thickness can typically be 500 nm or less.

In the semiconducting layer of the present invention, two or more chemical formulas 1-9 can be used.<img file="TW200529483A_D0246.tif" />Compound. Two or more organic binders of the present invention can be used in addition to or instead of the semiconductive layer.

As mentioned above, the present invention further provides a method for preparing an organic semiconducting layer, which includes (i) containing multiple<img file="TW200529483A_D0247.tif" />A liquid layer of a mixture of a compound, an organic binder resin or its precursor, and an optional solvent is deposited on the substrate, and (ii) a solid layer of the organic semiconducting layer is formed from the liquid layer.

In this method, the solid layer can be formed by evaporating the solvent and/or by reacting (if present) a binder resin precursor to form the binder resin in situ. The substrate may include any underlying component layers, electrodes, or individual substrates such as, for example, silicon wafers or polymer substrates.

In a specific embodiment of the present invention, the adhesive can be alignable, for example, can form a liquid crystal phase. In this case, the adhesive can help a lot<img file="TW200529483A_D0248.tif" />The alignment, such as making more<img file="TW200529483A_D0249.tif" />The main chain is preferentially aligned in the direction of charge transport. Suitable methods for aligning the adhesive include methods for aligning polymeric organic semiconductors, such as those described in WO 03/007397 (Plastic Logic).

The present invention also provides the use of semi-conductive formulations or layers in electronic devices. The formula can be used as a high-mobility semi-conductive material in various components and devices. The formulation can be used, for example, in the form of a semiconducting layer or film. Therefore, in another aspect, the present invention provides a semiconducting layer for use in electronic devices, which layer includes the formulation according to the present invention. This layer or film can be less than about 30 microns. For various electronic component applications, the thickness can be less than about 1 micron thick. The layer can be deposited on, for example, a part of the electronic component using any of the aforementioned solution coating or printing techniques.

The formulation can be used in field-effect transistors (FET), for example as a layer or film, for example as a semiconducting channel, used in organic light-emitting diodes (OLED), for example as a hole or electron injection or transport layer or electroluminescence Layers are used in photodetectors, chemical detectors, photovoltaic cells (PV), capacitor sensors, logic circuits, displays, memory components and the like. The formula can also be used in electronic photography (EP) devices. The formula is to form the layer or film in the aforementioned device or device by solution coating, so as to provide the advantages of cost and manufacturing diversity. The improved charge carrier mobility of the formulation of the present invention allows these devices or devices to operate faster and/or more efficiently. The formulations and layers of the present invention are particularly suitable for use as semiconducting channels in OFETs of organic field effect transistors. Therefore, the present invention also provides an organic field-effect transistor (OFET), which includes a source electrode, a drain electrode, and an organic semiconducting channel connecting the source and drain electrodes, wherein the organic semiconducting channel includes the organic semiconducting channel according to the present invention. Conductive layer. Other characteristics of OFET are well known to those who are familiar with the art.

Now explain the definitions and explanations of some terms used in this article.

When a series of labels appear in the chemical formula in the text (e.g. R₁, R₂Etc.) or an index (such as "n"), it indicates that it represents a series of groups or values, and it is called "independent in each case", which indicates that each indicator and/or index can represent each other independently Specifically, any of these groups listed independently in each reproduction unit, independently in each chemical formula, and/or independently on each group that is appropriately substituted. Therefore, in each of these examples, many different groups can be singly designated (e.g. R₅)Express.

As used herein, the terms "substituent", "substituted", "optionally substituted" and/or "optionally substituted" (unless followed by a series of other substituents) indicate at least of the following groups One (or substituted by these groups): silyl group, sulfonic acid group, sulfonyl group, methionine group, amino group, imino group, nitrogen group, mercapto group, cyano group, nitro group, halo group, C_1-4Alkyl, C_6-12Aryl, C_1-4Alkoxy, hydroxyl, and/or combinations thereof. These optional groups may include all chemically possible combinations in the same group and/or plural (preferably two) of the aforementioned groups (for example, if the amine group and the sulfonyl group are directly connected to each other, they represent an amine Sulfaji root). Preferred optional substituents include: C_1-4Alkyl; methoxy and/or ethoxy (any of which may be substituted with at least one halo group as required); amine group (which may be substituted with at least one methyl and/or ethyl group as required); and/ Or halo.

The term "carbon-based" as used herein refers to any monovalent or multivalent organic radical, which includes at least one carbon atom, does not have any non-carbon atoms (for example -CC-), or optionally combined with at least one other non-carbon atom Combination of carbon atoms (e.g., alkoxy, carbonyl, etc.).

The terms "hydrocarbyl", "hydrocarbon group", etc. may be used interchangeably in the text. The hydrocarbyl group may be substituted if necessary. The hydrocarbyl group may also include at least one of the following heteroatom-containing groups: an oxy group, a thio group, a sulfinyl group, a sulfonyl group, an amino group, an imino group, a nitrogen group, and/or a combination thereof.

The terms "alkyl", "aryl", etc. used in the text, when applicable, can be easily substituted by terms indicating different degrees of valence, such as multivalent species (eg, alkylene, aryl, etc.) .

The term "halo" as used herein refers to fluoro, chloro, bromo and iodo.

Unless clearly indicated in the text, groups in the text that include a chain of three or more carbon atoms indicate that all or part of the chain may be straight, branched and/or form a ring (including spiro and/or fused rings). Group.

Unless clearly indicated in the text, the plural terms used in the text should be interpreted as including the singular form and vice versa.

In the description of this specification and the scope of the patent application, the words "include" and "include" and word variations, for example, "have" and "include" mean "including but not limited to", and they are not intended to (and do not) exclude Other ingredients.

It should be understood that modifications to the foregoing specific embodiments of the present invention can be made within the scope of the present invention. Unless otherwise specified, the features disclosed in this specification can be replaced by alternative features that provide the same, equivalent, or similar use. Therefore, unless otherwise stated, the disclosed features are only an example of a general series of equivalent or similar features.

All the features disclosed in this specification can be combined in any combination, except that at least some of these features and/or steps are mutually exclusive combinations. More specifically, the preferred features of the present invention can be applied to all aspects of the present invention, and they can be used in any combination. Likewise, features described in non-basic combinations can be used individually (rather than in combination).

It should be understood that many of the features described above, especially the many features of the preferred embodiment, are themselves inventive, and not just part of a specific embodiment of the present invention. Independent protection for these features can be sought in addition to or in place of any currently claimed invention.

The present invention will now be described in more detail with reference to the following examples. These examples are only illustrative and do not limit the scope of the present invention.

<b>Example</b>

<b>Synthesis of organic semiconductor materials</b>

<b>1. 6,13-bis(triisopropylsilylethynyl) five</b><img file="TW200529483A_D0250.tif" /><b>-Synthesis of compound 1</b>

<chemistry general="n"><img file="TW200529483A_D0251.tif" /></chemistry>

The isopropyl magnesium chloride (2 M THF solution (with 6,13-penta<img file="TW200529483A_D0252.tif" />Quinone meter (10 molar equivalents)) was added to a flame-dried flask equipped with a mechanical stirrer, nitrogen inlet and outlet, condenser and threaded serum plug. Use a cold water bath as a cold trap to cool the solution to absorb any exothermic heat during the addition of triisopropylsilyl acetylene. The triisopropylsilyl acetylene (in 6,13-penta<img file="TW200529483A_D0253.tif" />10.1 molar equivalent of quinone) was added dropwise to the reaction flask within 30 minutes, and then THF (10 ml of TIPS acetylene per 10 millimoles) was added. The cold water bath was removed, and the solution was heated at 60°C for 20 minutes. The flask was then cooled to room temperature. Will be 6,13-five<img file="TW200529483A_D0254.tif" />Quinone (1 molar equivalent) is added to Grignard's reagent, and the resulting cloudy suspension is heated at 60°C until the reaction appears to be complete according to HPLC (up to 3 hours). Allow the flask to cool to room temperature. A 10% HCl aqueous solution saturated with tin(II) chloride is carefully added to the brown/red reaction solution until the solution no longer exotherms when it is added. (It was noted that when tin(II) chloride solution was added, the reaction solution turned from brown/red to dark blue). The resulting solution was heated at 60°C for 30 minutes before cooling to room temperature. This crude mixture was separated from the water/DCM mixture, and the organic phase was dissolved in magnesium sulfate (MgSO₄) Was dried on top, and concentrated in vacuo to obtain a blue/black solid. Purification by column chromatography (silica gel, 5% DCM in hexane) followed by recrystallization from acetone gave the title compound as a dark blue plate.

<b>2. Synthesis of 6,13-bis(triisopropylsilyl)ethynyl penta</b><img file="TW200529483A_D0255.tif" /><b>-Another approach to compound 1</b>

<chemistry general="n"><img file="TW200529483A_D0256.tif" /></chemistry>

(Triisopropylsilyl)acetylene (6 molar equivalents (2.18 ml, 9.72 mmol)) and tetrahydrofuran (THF) (15 ml) were added to the flame-dried flask, and the solution was cooled to- 78°C. Then a 2.5 M hexane solution of n-butyllithium (5.5 molar equivalents (3.56 ml, 8.91 mmol)) was added dropwise within 20 minutes. The resulting solution was stirred at -78°C for an additional 45 minutes. Join 6, 13-Fri<img file="TW200529483A_D0257.tif" />Quinone (1 molar equivalent (0.50 g, 1.62 mmol)), and the reaction mixture was allowed to warm to room temperature and stirred overnight. Then add SnCl at room temperature₂Saturated 10% HCl aqueous solution (5 mL), and the reaction mixture was stirred at 50°C for 30 minutes. When cooling, add 2 M Na₂CO₃Aqueous solution (5 mL), and the resulting crude solution was filtered through diatomaceous earth, and then concentrated in vacuo. Purified by chromatography (flash silica, hexane:DCM, 95:5), and then washed with acetone to obtain a dark blue powder of the title compound (0.73 g, 70%), and its purity measured by HPLC was greater than 99%.¹H NMR(CDCl₃)δ 9.30(4H,s,H-Ar), 7.95(4H,m,H-Ar), 7.41(4H,m,H-Ar) and 1.42ppm(42H,m,H-aliphatic);¹³C NMR(CDCl₃)δ 132.48, 130.83, 128.89, 126.52, 126.23, 118.56, 107.38, 104.90, 19.22 and 11.89ppm.

<b>3. 2,3,9,10-Tetramethyl-6,13-bis(triisopropylsilylethynyl)penta</b><img file="TW200529483A_D0258.tif" /><b>-Synthesis of compound 4</b>

<b>3a. Synthesis of 4,5-Dimethylphthalaldehyde-Compound 2</b>

<chemistry general="n"><img file="TW200529483A_D0259.tif" /></chemistry>

To a 2 M solution (26.5 ml, 53.0 millimoles, 2.2 molar equivalents) of oxalic chloride dissolved in dichloromethane (DCM) cooled to -78°C was added dimethyl sulfoxide (DMSO) (7.5 ML, 105.8 mmol, 4.4 mol equivalent) dissolved in DCM (10 mL). The solution was stirred at -78°C for 5 minutes, and 4,5-dimethylbenzene-1,2-dimethanol (4.0 g, 24.1 mmol, 1.0 molar equivalent) was added dropwise and dissolved in DCM-DMSO The solution in the mixture (2ml-4ml). The solution was stirred at -78°C for 1 hour, and triethylamine (20 mL) was slowly added at -78°C. The reaction mixture was stirred at -78°C for 10 minutes and slowly warmed to room temperature. Ice cold water (100 mL) was added to the reaction mixture, and the aqueous layer was extracted with DCM (3 times 100 mL). Combine the organic parts, dry over magnesium sulfate, filter and concentrate in vacuo to obtain a brown oil. Purified by silica gel column chromatography (eluent: hexane-ethyl acetate 8:2) to obtain the title compound as white needles (3.2 g, 82%).¹H NMR(300.13 MHz, CDCl₃)δ(ppm) 2.42(s, 6H), 7.73(s, 2H), 10.50(s, 2H).

<b>3b. 2,3,9,10-tetramethyl-6,13-penta</b><img file="TW200529483A_D0260.tif" /><b>Quinone-Synthesis of Compound 3</b>

<chemistry general="n"><img file="TW200529483A_D0261.tif" /></chemistry>

At room temperature in 4,5-dimethylphthalaldehyde (compound 2) (1.59 g, 9.8 millimoles, 2 mole equivalent) and 1,4-cyclohexanedione (0.54 g, 4.8 millimoles, 1 molar equivalent) was dissolved in ethanol (150 ml) and 5% NaOH aqueous solution (3 ml) was added. The reaction mixture was stirred at room temperature for 30 minutes, and then warmed to 60°C. After 1 hour at 60°C, the reaction mixture was allowed to cool to room temperature. The resulting precipitate was filtered and washed with water (25 mL), ethanol (50 mL) and ether (50 mL) to obtain the title compound as a yellow powder (1.63 g, 93%). IR (selection band) 1672 (quinone), 1579, 1452, 1396, 1221, 738 cm^-1。

<b>3c. 2,3,9,10-tetramethyl-6,13-bis(triisopropylsilylethynyl) five</b><img file="TW200529483A_D0262.tif" /><b>-Synthesis of compound 4</b>

<chemistry general="n"><img file="TW200529483A_D0263.tif" /></chemistry>

To a solution of triisopropylsilylacetylene (3.7ml, 16.4mmol, 6molequivalent) dissolved in tetrahydrofuran (THF) (100ml) cooled to -78°C, n-butyllithium was added dropwise 2.5 M solution in hexane (6 mL, 15 millimoles, 5.5 mole equivalents). Stir the solution at -78°C for 45 minutes, and add 2,3,9,10-tetramethyl-6,13-penta<img file="TW200529483A_D0264.tif" />Quinone (Compound 3) (1 g, 2.7 millimoles, 1 mole equivalent). The reaction mixture was warmed up and stirred at room temperature overnight. Add SnCl at room temperature₂Saturated 10% HCl aqueous solution (10 mL), and the reaction mixture was stirred at 50°C for 45 minutes. When cooling, add 2 M Na₂CO₃Aqueous solution (10 mL), and the resulting solution was stirred with diatomaceous earth for 5 minutes. The solution was filtered through celite and concentrated in vacuo to a dark blue solid. Purified by silica gel column chromatography (eluent, hexane:DCM 6:4), and then washed with acetone to obtain a dark blue powder of the title compound (0.8 g, 42%). Its purity measured by HPLC is greater than 99%.¹H NMR(300.13 MHz, CDCl₃)δ(ppm)1.36-1.39(m,42H), 7.67(s,4H), 9.12(s,4H);¹³C NMR(125.77 MHz, CDCl₃)δ(ppm) 11.72, 19.04, 20.56, 105.11, 106.23, 117.68, 124.49, 127.09, 130.42, 131.84, 136.37.

<b>4. 5,11-Bis(triisopropylsilylethynyl)anthra[2,3-<i>b</i>：6,7-<i>b'</i>]Dithiophene-compound 7 and 5,11-bis(triisopropylsilylethynyl)anthra[2,3-<i>b</i>：7,6-<i>b'</i>] Dithiophene-Synthesis of Compound 8</b>

<b>4a. Anthrao[2,3-<i>b</i>：6,7-<i>b'</i>]Dithiophene-5,11-dione-compound 5 and anthra[2,3-<i>b</i>：7,6-<i>b'</i>]Dithiophene-5,11-diketone-Synthesis of compound 6</b>

<chemistry general="n"><img file="TW200529483A_D0265.tif" /></chemistry>

At room temperature, 5% NaOH aqueous solution (3 mL) was added to thiophene-2,3-dicarbaldehyde (1.00 g, 7.1 millimoles, 2 molar equivalents) and 1,4-cyclohexanedione (0.40 g, 3.6 millimoles, 1 mole equivalent) dissolved in ethanol (100 ml). The reaction mixture was stirred at room temperature for 30 minutes, and then warmed to 60°C. After 1 hour at 60°C, the reaction mixture was allowed to cool to room temperature. The resulting precipitate was filtered and washed with water (20 mL), ethanol (40 mL) and ether (40 mL) to obtain the title compound as a yellow powder (1.02 g, 89%). IR (selection band) 1667 (quinone), 1573, 1318, 1283 cm^-1。

<b>4b. 5,11-bis(triisopropylsilylethynyl)anthra[2,3-<i>b</i>：6,7-<i>b'</i>]Dithiophene-compound 7 and 5,11-bis(triisopropylsilylethynyl)anthra[2,3-<i>b</i>：7,6-<i>b'</i>] Dithiophene-Synthesis of Compound 8</b>

<chemistry general="n"><img file="TW200529483A_D0266.tif" /></chemistry>

To a solution of triisopropylsilyl acetylene (2.1 ml, 9.4 millimoles, 6 mole equivalents) dissolved in tetrahydrofuran (THF) (50 ml) cooled to -78°C, n-butyl lithium was added dropwise 2.5 M solution in hexane (3.4 mL, 8.5 millimoles, 5.5 molar equivalents). The solution was stirred at -78°C for 45 minutes, and anthradithiophene-5,11-dione (compounds 5 and 6) (0.5 g, 1.6 millimoles, 1 molar equivalent) was added. The reaction mixture was warmed up and stirred at room temperature overnight. Add SnCl at room temperature₂Saturated 10% HCl aqueous solution (5 mL), and the reaction mixture was stirred at 50°C for 45 minutes. When cooling, add 2 M Na₂CO₃Aqueous solution (5 mL), and the resulting solution was stirred with diatomaceous earth for 5 minutes. The solution was filtered through celite and concentrated in vacuo to a dark red solid. Purified by silica gel column chromatography (eluent, hexane:DCM 8:2), and then washed with acetone to obtain dark red powder of the title compound (0.45 g, 44%). Its purity measured by HPLC is greater than 99% (co-extraction of the same side and opposite side isomers).¹H NMR(500.13 MHz, CDCl₃)δ(ppm)1.37-1.39(s,42H), 7.42(d,J=5.50 Hz,2H), 7.54(dd,J₁=5.50,J₂=2.00 Hz,2H), 9.15(s,2H), 9.19(s,2H);¹³C NMR(125.77 MHz, CDCl₃)δ(ppm) 11.26, 11.65, 18.74, 18.96, 104.13, 104.20, 105.61, 105.89, 106.16, 117.62, 118.92, 120.02, 120.06, 121.31, 121.37, 123.75, 129.76, 129.78, 129.85, 129.88, 129.96, 130.06, 139.46 , 139.61, 139.96, 140.06.

<b>5. 6,13-bis(trimethylsilyl)ethynyl penta</b><img file="TW200529483A_D0267.tif" /><b>-Synthesis of compound 9</b>

<chemistry general="n"><img file="TW200529483A_D0268.tif" /></chemistry>

(Trimethylsilyl)acetylene (6 molar equivalents (13.7 mL, 97.3 mmol)) and tetrahydrofuran (THF) (110 mL) were added to the flame-dried flask, and the solution was cooled to -78 °C. Then a 2.5 M hexane solution of n-butyllithium (5.5 molar equivalents (36.0 ml, 89.2 mmol)) was added dropwise within 20 minutes. The resulting solution was stirred at -78°C for an additional 45 minutes. Then join 6,13-Fri<img file="TW200529483A_D0269.tif" />Quinone (1 molar equivalent (5.0 g, 16.2 mmol)), and the reaction mixture was allowed to warm to room temperature and stirred overnight. Then add SnCl at room temperature₂Saturated 10% HCl aqueous solution (50 mL), and the reaction mixture was stirred at 50°C for 30 minutes. When cooling, add 2 M Na₂CO₃Aqueous solution (50 mL), and the resulting crude solution was filtered through Celite, and then concentrated in vacuo. Purified by chromatography (flash silica, hexane:DCM, 80:20), and then washed with acetone to obtain a dark blue powder of the title compound (3.8 g, 50%), and its purity measured by HPLC is greater than 99%.¹H NMR(CDCl₃)δ 9.21 (4H, s, H-Ar), 8.05 (4H, m, H-Ar), 7.42 (4H, m, H-Ar) and 0.53 ppm (18H, s, H-aliphatic).

<b>6. 6,13-bis(triethylsilyl)ethynylpenta</b><img file="TW200529483A_D0270.tif" /><b>-Synthesis of compound 10</b>

<chemistry general="n"><img file="TW200529483A_D0271.tif" /></chemistry>

Isopropyl magnesium chloride (2 M THF solution; 10 molar equivalents (13.7 mL, 27.4 mmol)) and tetrahydrofuran (THF) (60 mL) were added to the flame-dried flask. Then triethylsilyl acetylene (10 molar equivalents, 5.6 ml, 31.3 millimoles) was added dropwise. The mixture was then heated at reflux for 20 minutes. Allow the resulting solution to cool to room temperature, and add 6,13-five<img file="TW200529483A_D0272.tif" />Quinone (1 molar equivalent (1.0 g, 3.24 millimoles)). The reaction mixture was then heated at reflux for 1 hour before cooling to room temperature. Add SnCl at room temperature₂Saturated 10% HCl aqueous solution (50 mL), and the reaction mixture was stirred at 50°C for 30 minutes. When cooled, add saturated potassium bicarbonate solution (KHCO₃) (25 mL), and the resulting crude solution was filtered through diatomaceous earth, and then concentrated in vacuo. By rapid column chromatography (eluent 20% CH₂Cl₂: Hexane) purification, followed by washing with acetone to obtain a dark blue powder of the title compound (1.1 g, 61%), and its purity measured by HPLC is greater than 99%.¹H NMR(300MHz, CDCl₃)δ 9.25 (4H, s, H-Ar), 8.00 (4H, m, H-Ar), 7.40 (4H, m, H-Ar), 1.30 (18H, t, J=6.0 Hz, SiCH₂C<b>H</b>_<b>3</b>), 0.98ppm (12H, q, J=6.0Hz, SiC<b>H</b>_<b>2</b>CH₃)。

<b>7. 6,13-bis(4'-pentphenyl)ethynylpenta</b><img file="TW200529483A_D0273.tif" /><b>-Compound 11</b>

<chemistry general="n"><img file="TW200529483A_D0274.tif" /></chemistry>

Isopropyl magnesium chloride (2 M THF solution; 10 molar equivalents (32.4 mL, 64.8 mmol)) and tetrahydrofuran (THF) (60 mL) were added to the flame-dried flask. Then 1-ethynyl-4-pentylbenzene (10 molar equivalents, 12.4 ml, 63.7 millimoles) was added dropwise. The mixture was then heated at reflux for 20 minutes. Allow the resulting solution to cool to room temperature, and add five<img file="TW200529483A_D0275.tif" />Quinone (1 molar equivalent (2.0 g, 6.5 millimoles)). The reaction mixture was then heated at reflux for 30 minutes. The mixture was allowed to cool to room temperature. Add SnCl at room temperature₂Saturated 10% HCl aqueous solution (20 mL), and the reaction mixture was stirred at 50°C for 30 minutes. When cooling, slowly add saturated Na₂CO₃Solution (50 mL). Transfer the material to a 1 liter separatory funnel, then add water (100 ml) and CH₂Cl₂(50 ml). Separate the organic and water phases, and use CH₂Cl₂(3×50 mL) The aqueous phase was extracted. The combined organic phase was then washed with water (100 mL), filtered through Whatman No. 1 filter paper, and concentrated to a blue solid. This material was stirred with acetone (50 mL) and filtered to obtain a blue solid (3.0 g, 75%). After rapid column chromatography (quick silica, eluent 40% CH₂Cl₂: Hexane) Purify 1 g of this material to obtain a blue solid of the product (0.8 g, 80% recovery), the purity of which is greater than 99% as measured by HPLC.¹H NMR(300 MHz, CDCl₃)δ 9.20(4H,s,H-Ar), 7.90(4H,m,H-Ar), 7.35(4H,m,H-Ar), 2.73(4H,t,J=6.0Hz,-C CC<b>H</b>_<b>2</b>-), 1.72(4H,m,CCCH₂C<b>H</b>_<b>2</b>-), 1.40(8H,m,C CCH₂CH₂C<b>H</b>_<b>2</b>C<b>H</b>_<b>2</b>-), 0.95ppm (12H, t, J=3.0Hz, CH₂C<b>H</b>_<b>3</b>)。

<b>8. Naphtho[2,1,8-qra] naphthalene</b><img file="TW200529483A_D0276.tif" /><b>-7,12-(Triisopropylsilyl)ethynyl-Synthesis of Compound 12</b>

<chemistry general="n"><img file="TW200529483A_D0277.tif" /></chemistry>

(Triisopropylsilyl)acetylene (6 molar equivalents (2.03 ml, 9.03 mmol)) and tetrahydrofuran (THF) (50 ml) were added to the flame-dried flask, and the solution was cooled to -78°C. A 2.5 M hexane solution of n-butyllithium (5.5 molar equivalents (5.16 ml, 8.25 mmol)) was added dropwise within 20 minutes. The resulting solution was stirred at -78°C for an additional 45 minutes. Then add naphtho[2,1,8-qra]naphthalene<img file="TW200529483A_D0278.tif" />-7,12-dione (1 molar equivalent (0.50 g, 1.50 mmol)), and the reaction mixture was allowed to warm to room temperature and stirred overnight. Add SnCl at room temperature₂Saturated 10% HCl aqueous solution (10 mL), and the reaction mixture was stirred at 50°C for 30 minutes. When cooling, add 2 M Na₂CO₃Aqueous solution (5 mL), and the resulting crude solution was filtered through diatomaceous earth, and then concentrated in vacuo. Purified by chromatography (flash silica, hexane:DCM, 95:5), and then washed with acetone to obtain a red powder of the title compound (0.23 g, 23%), and its purity measured by HPLC was greater than 99%.¹H NMR(CDCl₃)δ 11.09 (1H, d, H-Ar), 9.30 (1H, s, H-Ar), 9.08 (1H, m, H-Ar), 8.80 (1H, m, H-Ar), 8.20 (2H, m,H-Ar), 7.95(2H,m,H-Ar), 7.82(2H,m,H-Ar), 7.71(2H,m,H-Ar) and 1.47-1.25ppm(42H,m,H -Aliphatic).

<b>9. 5,14-(Triisopropylsilyl)acetylene penta</b><img file="TW200529483A_D0279.tif" /><b>-Synthesis of compound 14</b>

<b>9a. 5,14-Fri</b><img file="TW200529483A_D0280.tif" /><b>Quinone-Synthesis of Compound 13</b>

<chemistry general="n"><img file="TW200529483A_D0281.tif" /></chemistry>

Add 2,3-naphthalaldehyde (1 molar equivalent (0.29 g, 1.57 millimoles)) and 1,4-dihydroxynaphthalene (1 molar equivalent (0.25 g, 1.57 millimoles)) to the flame In a dry flask, flush these reagents with nitrogen for 15 minutes before adding anhydrous pyridine (5 mL). The resulting solution was stirred at 120°C for 24 hours. When cooled, the solid product was filtered off, washed successively with methanol (10 mL), 10% copper sulfate solution (10 mL), water (10 mL) and acetone (10 mL), and dried in a vacuum oven. The product was an orange/brown solid (0.14 g, 29%), and its purity measured by HPLC was greater than 90%.¹H NMR(D8-THF)δ 9.09(2H,s,H-Ar), 8.87(2H,s,H-Ar), 8.38(2H,m,H-Ar), 8.15(2H,m,H-Ar) ), 7.87 (2H, m, H-Ar) and 7.61 ppm (2H, m, H-Ar).

<b>9b. 5,14-(triisopropylsilyl)acetylene penta</b><img file="TW200529483A_D0282.tif" /><b>-Synthesis of compound 14</b>

<chemistry general="n"><img file="TW200529483A_D0283.tif" /></chemistry>

(Triisopropylsilyl)acetylene (6 molar equivalents (1.31 ml, 5.84 mmol)) and tetrahydrofuran (THF) (10 ml) were added to the flame-dried flask, and the solution was cooled to- 78°C. A 2.5 M hexane solution of n-butyllithium (5.5 molar equivalents (3.34 ml, 5.35 mmol)) was added dropwise within 20 minutes. The resulting solution was stirred at -78°C for an additional 45 minutes. Then join 5,14-Fri<img file="TW200529483A_D0284.tif" />Quinone (compound (13)) (1 molar equivalent (0.30 g, 0.97 mmol)), and the reaction mixture was warmed to room temperature and stirred overnight. Then add SnCl at room temperature₂Saturated 10% HCl aqueous solution (5 mL), and the reaction mixture was stirred at 50°C for 30 minutes. When cooling, add 2 M Na₂CO₃Aqueous solution (5 mL), and the resulting crude solution was filtered through diatomaceous earth, and then concentrated in vacuo. Purified by chromatography (rapid silica, hexane:DCM, 90:10), and then washed with acetone to obtain a dark blue powder of the title compound (0.22 g, 35%), and its purity measured by HPLC is greater than 99%.¹H NMR(CDCl₃)δ 9.58(2H,s,H-Ar), 8.68(2H,s,H-Ar), 8.55(2H,m,H-Ar), 8.00(2H,m,H-Ar), 7.50(2H, m, H-Ar), 7.39 (2H, m, H-Ar) and 1.45-1.25 ppm (42H, m, H-aliphatic).

<b>10. 1,8-Difluoro-6,13-bis(triisopropylsilylethynyl)penta</b><img file="TW200529483A_D0285.tif" /><b>-Compound 19 and 1,11-difluoro-6,13-bis(triisopropylsilylethynyl) penta</b><img file="TW200529483A_D0286.tif" /><b>-Synthesis of compound 20</b>

<b>10a. Synthesis of 3-fluorobenzene-1,2-dimethanol-compound 15</b>

<chemistry general="n"><img file="TW200529483A_D0287.tif" /></chemistry>

LiAlH cooled to -78°C₄Solution (1 M in tetrahydrofuran) (54 ml, 54.0 millimoles, 2.0 mole equivalents) was added dropwise 3-fluorophthalic acid (5.0 g, 27.2 millimoles, 1 mole equivalent) in THF (25 Ml) in the solution. The reaction mixture was warmed to room temperature and then stirred at 70°C for 2 hours. 2 M sodium hydroxide solution (25 mL) was added to the resulting solution cooled at 0°C, followed by cold water (25 mL) and THF (50 mL). The reaction mixture was then further extracted with THF (3×50 mL). The organic parts were combined, washed with brine, dried over magnesium sulfate, filtered and concentrated in vacuo to obtain a pale yellow solid. Purification by recrystallization from acetone/hexane gave the title compound as white needles (3.3 g, 79%).¹H NMR(300.13 MHz, DMSO)δ(ppm)4.53(dd,J₁=5.50, J₂=2.00 Hz, 2H), 4.67(d,J=5.50 Hz, 2H), 4.98(t,J=5.50 Hz, 1H), 5.22(t,J=5.50 Hz, 1H), 7.00-7.10(m,1H ), 7.25-7.35 (m, 2H).¹⁹F NMR (282.38 MHz, DMSO) δ (ppm) -119.92 (s).¹³C NMR(75.48 MHz, CDCl₃)δ(ppm) 52.63, 60.07, 113.26, 122.81, 128.69, 144.02, 158.64, 161.87.

<b>10b. Synthesis of 3-Fluorophthalaldehyde-Compound 16</b>

<chemistry general="n"><img file="TW200529483A_D0288.tif" /></chemistry>

To a 2 M solution (11 ml, 22 millimoles, 2.2 molar equivalents) of oxalic chloride dissolved in dichloromethane (DCM) cooled to -78°C was added dimethyl sulfoxide (DMSO) (3.10) dropwise. ML, 44 millimoles, 4.4 mole equivalents) dissolved in DCM (10 mL). Then the solution was stirred at -78°C for 5 minutes, and 3-fluorobenzene-1,2-dimethanol (Compound 17) (1.55 g, 10 mmol, 1.0 molar equivalent) was added dropwise and dissolved in DCM-DMSO Solution in the mixture (1-2 ml). The solution was then stirred at -78°C for 1 hour, and triethylamine (25 mL) was slowly added at -78°C. The reaction mixture was then stirred at -78°C for 10 minutes, and slowly warmed to room temperature. Ice cold water (50 mL) was added to the reaction mixture, and the aqueous layer was extracted with DCM (3 times 50 mL). Combine the organic parts, dry over magnesium sulfate, filter and concentrate in vacuo to obtain a brown oil. Purification by distillation gave the title compound as a pale yellow solid (1.10 g, 73%).¹H NMR(300.13 MHz, CDCl₃)δ(ppm) 7.36-7.50(m, 1H), 7.69-7.79(m, 2H), 10.51(s, 1H), 10.57(s, 1H).¹⁹F NMR(282.38 MHz, CDCl₃)δ(ppm)-118.90(s).

<b>10c. 1,8-difluoro-6,13-penta</b><img file="TW200529483A_D0289.tif" /><b>Quinone-compound 17 and 1,11-difluoro-6,13-penta</b><img file="TW200529483A_D0290.tif" /><b>Quinone-Synthesis of Compound 18</b>

<chemistry general="n"><img file="TW200529483A_D0291.tif" /></chemistry>

At room temperature in 3-fluorophthalaldehyde (compound 18) (0.42 g, 2.8 millimoles, 2 mole equivalent) and 1,4-cyclohexanedione (0.15 g, 1.4 millimoles, 1 mole equivalent) ) In ethanol (45 mL) was added 5% NaOH aqueous solution (0.6 mL). The reaction mixture was stirred at room temperature for 30 minutes, and then warmed to 60°C. After 1 hour at 60°C, the reaction mixture was allowed to cool to room temperature. The resulting precipitate was filtered and washed with water (15 mL), ethanol (30 mL) and ether (30 mL) to obtain a yellow powder of the title compound (0.40 g, 87%), which was used in the prepared state.¹H NMR(300.13 MHz, CDCl₃, Trifluoroacetic acid)δ(ppm)7.35-7.47(m,1H), 7.72(td,J₁=8.03, J₂=5.32 Hz, 1H), 7.97 (d, J=8.22 Hz, 1H), 8.99-9.04 (m, 1H), 9.23-9.27 (m, 1H).¹⁹F NMR(282.38 MHz, CDCl₃, Trifluoroacetic acid)δ(ppm)-118.60(s). IR (selection band) 1681 (quinone), 1627, 1443, 1287, 791, 747 cm^-1。

<b>10d. 1,8-Difluoro-6,13-bis(triisopropylsilylethynyl)penta</b><img file="TW200529483A_D0292.tif" /><b>-Compound 19 and 1,11-difluoro-6,13-bis(triisopropylsilylethynyl) penta</b><img file="TW200529483A_D0293.tif" /><b>-Synthesis of compound 20</b>

<chemistry general="n"><img file="TW200529483A_D0294.tif" /></chemistry>

To a solution of triisopropylsilyl acetylene (1.2 mL, 5.3 mmol, 6 mol equivalent) dissolved in THF (30 mL) cooled to -78°C, n-butyl lithium in hexane was added dropwise 2.5 M solution (1.9 ml, 4.8 millimoles, 5.5 molar equivalents). Then the solution was stirred at -78°C for 45 minutes, and difluoro-6,13-penta<img file="TW200529483A_D0295.tif" />Quinone (compounds 17 and 18) (0.3 g, 0.9 millimoles, 1 mole equivalent). The reaction mixture was then warmed up and stirred at room temperature overnight. Add SnCl at room temperature₂Saturated 10% HCl aqueous solution (3 mL), and the reaction mixture was stirred at 50°C for 45 minutes. When cooling, add 2 M Na₂CO₃Aqueous solution (3 mL). The resulting solution was filtered through Celite and concentrated in vacuo to a dark red solid. Purified by silica gel column chromatography (eluent, hexane:DCM 9:1), followed by washing with acetone, a dark blue powder of the title compound (0.38 g, 65%) was obtained. The purity measured by HPLC was greater than 99% (co-solvent extraction of isomers on the same side and opposite side).¹H NMR(500.13 MHz, CDCl₃)δ(ppm)1.35-1.39(m,42H), 7.03-7.09(m,2H), 7.25-7.37(m,2H), 7.77(d,J=8.77 Hz,2H), 9.33(s,2H) , 9.60(s,2H);¹³C NMR(75.48 MHz, CDCl₃)δ(ppm) 11.64, 18.88, 18.93, 104.10, 104.24, 107.71, 107.75, 108.02, 108.24, 120.27, 124.62, 125.27, 125.37, 126.35, 126.47, 130.43, 130.88, 157.27, 160.67.

<b>11. 2,3,9,10-tetrafluoro-6,13-bis(triisopropylsilylethynyl)penta</b><img file="TW200529483A_D0296.tif" /><b>-Synthesis of compound 24</b>

<b>11a. Synthesis of 4,5-Difluorobenzene-1,2-Dimethanol-Compound 21</b>

<chemistry general="n"><img file="TW200529483A_D0297.tif" /></chemistry>

LiAlH cooled to -78°C₄Solution (1 M in tetrahydrofuran) (11 ml, 11.0 millimoles, 2.0 mole equivalent) was added dropwise 4,5-difluorophthalic anhydride (1.0 g, 5.4 millimoles, 1 mole equivalent) in Solution in THF (5 mL). The reaction mixture was warmed to room temperature and then stirred at 70°C for 2 hours. 2 M sodium hydroxide solution (5 mL) was added to the resulting solution cooled to 0°C, followed by cold water (5 mL) and THF (10 mL). The reaction mixture was then further extracted with THF (3 times 20 mL). The organic parts were combined, washed with brine, dried over magnesium sulfate, filtered and concentrated in vacuo to obtain a pale yellow solid. Purification by recrystallization from acetone/hexane gave the title compound as light yellow needles (0.8 g, 85%).¹H NMR (300.13 MHz, DMSO) δ (ppm) 4.47 (d, J=5.30, 4H), 5.26 (t, J=5.30 Hz, 2H), 7.36 (t, J=10.10 Hz, 2H).¹⁹F NMR (282.38 MHz, DMSO) δ (ppm)-142.27 (s).

<b>11b. Synthesis of 4,5-Difluorophthalaldehyde-Compound 22</b>

<chemistry general="n"><img file="TW200529483A_D0298.tif" /></chemistry>

To a 2 M solution (4.5 ml, 8.8 millimoles, 2.2 molar equivalents) of oxalic chloride dissolved in dichloromethane (DCM) cooled to -78°C was added dimethyl sulfoxide (DMSO) (1.25 Ml, 17.7 millimoles, 4.4 mole equivalents) dissolved in DCM (5 ml). The solution was stirred at -78°C for 5 minutes, and 4,5-difluorobenzene-1,2-dimethanol (Compound 21) (0.70 g, 4.0 millimoles, 1.0 molar equivalent) was added dropwise and dissolved in DCM / DMSO mixture (1-2 ml) solution. The solution was stirred at -78°C for 1 hour, and triethylamine (15 mL) was slowly added at -78°C. The reaction mixture was stirred at -78°C for 10 minutes, and slowly warmed to room temperature. Ice cold water (25 mL) was added to the reaction mixture, and the aqueous layer was extracted with DCM (3 times 30 mL). The organic parts are combined, dried over magnesium sulfate, filtered and concentrated in vacuo to obtain a yellow oil. Purified by silica gel column chromatography (eluent, hexane:DCM 2:8) to obtain the title compound as a pale yellow solid (0.58 g, 85%).¹H NMR(300.13 MHz, CDCl₃)δ(ppm) 7.83(t, J=9.00 Hz, 2H), 10.49(s, 2H).¹⁹F NMR(282.38 MHz, CDCl₃)δ(ppm)-127.10(s).

<b>11c. 2,3,9,10-tetrafluoro-6,13-penta</b><img file="TW200529483A_D0299.tif" /><b>Quinone-Synthesis of Compound 23</b>

<chemistry general="n"><img file="TW200529483A_D0300.tif" /></chemistry>

At room temperature in 4,5-difluorophthalaldehyde (compound 22) (0.48 g, 2.8 millimoles, 2 mole equivalent) and 1,4-cyclohexanedione (0.16 g, 1.4 millimoles, 1 5% NaOH aqueous solution (0.6 mL) was added to the solution in ethanol (40 mL). The reaction mixture was stirred at room temperature for 30 minutes, and then warmed to 60°C. After 1 hour at 60°C, the reaction mixture was allowed to cool to room temperature. The resulting precipitate was filtered and washed with water (15 mL), ethanol (30 mL) and ether (30 mL) to obtain the title compound as a yellow powder (0.35 g, 64%), which was used as it was prepared .

<b>11d. 2,3,9,10-tetrafluoro-6,13-bis(triisopropylsilylethynyl) five</b><img file="TW200529483A_D0301.tif" /><b>-Synthesis of compound 24</b>

<chemistry general="n"><img file="TW200529483A_D0302.tif" /></chemistry>

To a solution of triisopropylsilyl acetylene (0.7 ml, 3.2 millimoles, 6 mole equivalents) dissolved in THF (20 ml) cooled to -78°C, n-butyl lithium in hexane was added dropwise 2.5 M solution (1.2 mL, 2.9 millimoles, 5.5 mole equivalents). The solution was stirred at -78°C for 45 minutes, and then 2,3,9,10-tetrafluoro-6,13-penta<img file="TW200529483A_D0303.tif" />Quinone (Compound 23) (0.2 g, 0.5 millimolar, 1 mole equivalent). The reaction mixture was then allowed to warm to room temperature overnight. Add SnCl at room temperature₂Saturated 10% HCl aqueous solution (2 mL), and the reaction mixture was stirred at 50°C for 45 minutes. When cooling, add 2 M Na₂CO₃Aqueous solution (2 mL). The resulting solution was filtered through Celite and concentrated in vacuo to a dark blue solid. Purified by silica gel column chromatography (eluent, hexane:DCM 9:1), followed by washing with acetone, a dark blue powder of the title compound (0.13 g, 35%) was obtained.¹H NMR(300.13 MHz, CDCl₃)δ(ppm)1.32-1.44(m,42H), 7.63(t,J=9.00 Hz,4H), 9.20(t,4H);¹⁹F NMR(282.38 MHz, CDCl₃)δ(ppm)-134.01(s).

<b>Examples 12 to 15-Mobility measurement of OFETs prepared in the presence and absence of (polymeric) binders</b>

<b>Measurement of field effect movement rate</b>

The technique described in Holland et al., J. Appl. Phys., Vol. 75, page 7954 (1994) was used to test the field effect mobility of the following organic semiconductor materials.

In the following embodiments, a test field effect transistor is fabricated by using standard techniques, such as shadow masking, to pattern PEN substrates with Pt/Pd source and drain electrodes. Compound 1 (Example 12) and Compound 4 (Example 14) blended with an inert polymeric binder resin (poly(α-methylstyrene) (p-αMS)) were used to prepare semiconductor formulations. Then, 1 part of the semiconductor formula was dissolved in 99 parts of solvent (toluene in Examples 12 and 13, 1,2-dichlorobenzene in Examples 14 and 15), and spin-coated on the substrate at 500 rpm for 18 seconds . To ensure complete drying, place the sample in an oven at 100°C for 20 minutes. For comparison, a thin film of a pure organic semiconductor compound (OSC) without a binder was coated on the substrate by spin coating (Comparative Example 13 of Compound 1 and Comparative Example 15 of Compound 4). Then these samples were also dried in an oven at 100°C for 20 minutes. The insulator material (Cytop 107 M, purchased from Asahi Glass) mix 3 parts to 2 parts of perfluorinated solvent (FC75, Acros catalog number 12380), and then spin-coated on the semiconductor to a thickness of typically about 1 micron. The sample was again placed in an oven at 100°C for 20 minutes to allow the solvent to evaporate from the insulator. Through evaporation through the baffle, gold gate contacts are defined on the device channel area. In order to measure the capacitance of the insulator layer, a number of devices composed of a non-patterned Pt/Pd base layer, an insulator layer prepared in the same way as the insulator layer on the FET device, and an upper electrode of a known shape were prepared. Use a handheld multimeter connected to the metal side of the insulator to measure the capacitance. Other defining parameters of transistors are the length of the drain and source electrodes facing each other (W=30 mm) and the distance between them (L=130 microns).

The voltage applied to the transistor is relative to the potential of the source electrode. In the case of a p-type gate material, when a negative potential is applied to the gate, positive charge carriers (holes) accumulate in the semiconductor on the other side of the gate dielectric. (For an n-channel FET, a positive voltage is applied). This is called accumulation mode. Capacitance of gate dielectric per unit area<i>C</i>_<i>l</i>Determine the amount of charge so caused. When the negative potential<i>V</i>_<i>DS</i>When applied to the drain, the accumulated carrier generates a source-drain current<i>I</i>_<i>DS</i>, It mainly depends on the density of the accumulated carrier, and more importantly, depends on the rate of movement in the source-drain channel. Geometric factors, such as the shape, size, and distance of the sink and source electrodes, also affect the current. Typically, a range of gate and drain voltages are scanned in device research. The source-drain current is described by Equation 1.

<maths><img file="TW200529483A_D0304.tif" /></maths>

in<i>V</i>_<i>0</i>System deviation voltage, and<i>I</i>_ΩIt is an ohmic current that has nothing to do with the gate voltage and is due to the limited conductivity of the material. Other parameters are described above.

Regarding the electrical measurement, the transistor sample is installed in the sample device. Use the Karl Suss PH100 mini-probe to connect the microprobes of the gate, drain and source electrodes. Connect it to the Hewlett-Packard 4155B parameter analyzer. The drain voltage is set to -5 volts, and the gate voltage is scanned from +20 to -60 volts and back to +20 volts in 1 volt steps. In accumulation, when |<i>V</i>_<i>G</i> |&gt;| <i>V</i>_<i>DS</i> |When the source-drain current varies with<i>V</i>_<i>G</i>Linear change. Therefore, the field effect movement rate can be expressed by Equation 2<i>I</i>_<i>DS</i>Correct<i>V</i>_<i>G</i>The gradient (S) is calculated.

<maths><img file="TW200529483A_D0305.tif" /></maths>

All field effect movement rates quoted below are calculated using this scheme (unless otherwise stated). When the field effect movement rate changes with the gate voltage, this value is regarded as the accumulation mode when |<i>V</i>_<i>G</i> |&gt;| <i>V</i>_<i>DS</i> |The highest value reached in the time plan. The values quoted in Table 4 are the average values of several elements (manufactured on the same substrate), and the sample size of the number of tested elements is also quoted in Table 4. FIG. 1 shows an example of the current-voltage and mobility-voltage characteristics of Embodiment 12. The forward and reverse scans illustrate the low current hysteresis of the component. The results show the excellent charge mobility of OFET devices when the adhesive is used in conjunction with the tested organic semiconductor materials. When no adhesive is used, there is a significant change in the measured mobility of components coated on the same substrate. This fact is reflected in the large standard deviation (% of the average value) of the mobility value of OFET coated on the same substrate.

<tables><img file="TW200529483A_D0306.tif" /></tables>

The results in Table 4 show that when the (polymeric) adhesive is used in the formulation of OFET devices, the mobility value and uniformity of OFET are substantially improved. The improvement of uniformity is explained by the small standard deviation of the ratio of the average value of the examples (Examples 12 and 14) with the adhesive as the result of the mobility. This is in contrast to Examples 13 and 15 that show large standard deviations (in proportion to the average value) without using a binder.

<b>Examples 16 to 26-OFET prepared using a range of polymeric binders</b><b>Mobility measurement</b>

The OFET was prepared using the method described with respect to Examples 12 to 15, except that a different polymeric binder was used.

<b>Table 5-Mobility measurement of OFET prepared using a range of polymeric adhesives</b><tables><img file="TW200529483A_D0307.tif" /></tables>Topas^TM 8007-e.g. Ticona (linear olefins and cyclic olefins (nor<img file="TW200529483A_D0308.tif" />Olefin) copolymer), (Examples 16 and 17); PS(1M)-polystyrene M_w=1,000,000, Aldrich catalog number 48,080-0, (Example 18); p-4-MS-poly-4-methylstyrene, Aldrich catalog number 18,227-3, (Example 19); PS-co-α MS -Polystyrene-co-α-methylstyrene, Aldrich catalog number 45,721-3, (Example 20); poly(vinyl cinnamate) Aldrich No: 18,264-8, (Example 21) PMMA-polymethyl Methyl acrylate Mn=797, (Example 22) PVP-poly-4-vinylphenol Aldrich catalog number 43,622-4, (Comparative Example 23); PVA-polyvinyl alcohol Aldrich catalog number 36,316-2, (Comparative Example 24); Poly(4-vinylbiphenyl) Aldrich catalog number 18,254-0, (Example 25);^aPolymer Handbook (3rd edition) Wiley and Sons (1989).^bManufacturer data^cIt is obtained by measuring the capacitance and thickness of the adhesive film between two metal electrodes, and then using the following relationship to calculate the dielectric constant ε: ε=<i>Cd</i>/E₀<i>A</i>Where C is the capacitance, d is the film thickness, E₀Is the permittivity of free space, and A is the area of the capacitor.^dFicker et al.,<i>J.Appl.Phys.,</i>2003 <i>94</i>(4),2638。^eStutzman et al.,<i>Science</i> 2003,<i>299,</i>1881。

The results in Table 5 show that the adhesive with a permittivity value greater than 3.3 significantly reduces the mobility value in the OFET device. Therefore, the preferred polymeric adhesive has a permittivity value lower than 3.3.

<b>Examples 27 to 28</b>

The OFET was prepared using the method described in the above Examples 12 to 15, except that the polymeric adhesive used was a semi-conductive material other than the insulating adhesive. The results are shown in Table 6.

<tables><img file="TW200529483A_D0309.tif" /></tables>In Table 6, poly(9-vinylcarbazole) was purchased from Aldrich, catalog number: 18,260-5 (Example 27).^＊-Refer to Schaffert RMIBM Journal of Res. And Devel. Vol 15 Nol, p79 (1971) c-has the same meaning as Table 5. PTAA1- is a triarylamine compound of chemical formula 18.

<chemistry general="n"><img file="TW200529483A_D0310.tif" /></chemistry>Chemical formula (18) where n=10.7 and Mn=3100(<i>Adv.Funct.Mater.</i>2003,<i>13</i>,No.13,p199-204).

The results in Table 6 indicate that semiconductive adhesives can also be used to obtain OFETs according to the present invention exhibiting excellent mobility values.

<b>Examples 29 to 31</b>

The OFET was prepared again using the method described with respect to Examples 12 to 15 above. However, in Examples 29 to 31, the ratio of OSC material to binder was changed. Example 12 is also included for comparison.

<tables><img file="TW200529483A_D0311.tif" /></tables>

The above results show that even when the ratio of OSC material to adhesive is 50:50, excellent mobility values for OFET devices can still be obtained.

<b>Examples 32 to 35-Mobility measurement of OFETs prepared using changes in solid content</b>

The OFET was prepared again using the method described with respect to Examples 12 to 15 above, except that the solid content of the formulation was changed.

<tables><img file="TW200529483A_D0312.tif" /></tables>