JP2011054774A - Method of manufacturing semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a semiconductor device by which selective coating using a template is performed even when a semiconductor material has a high molecular weight. <P>SOLUTION: In a state wherein a gate insulating film 2 and films of a source electrode 3c and a drain electrode 3d are formed on a substrate 1, a first self-assembled monolayer (first SAM film 5) having a perfluoroalkyl group is formed on a surface of the substrate 1. Then a region 5a of the first SAM film 5 to be coated with a polymeric organic semiconductor film is removed through ozone processing, and a second self-assembled monolayer (second SAM film 6) having a phenethyl group is formed in the region 5a. Then, the substrate 1 is preheated at 40°C, dipped in a poly(3-hexylthiophene)(P3HT) 0.5 wt.% dichlorobenzene solution 8 temperature-controlled to 40°C, and then lifted vertically to manufacture a thin film transistor. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for manufacturing a semiconductor device using an organic semiconductor material.

  In recent years, techniques using organic semiconductor materials for semiconductor devices such as thin film transistors have been studied. Since a semiconductor device using an organic semiconductor material can form a semiconductor film at a low temperature, it can be formed on a substrate having low heat resistance such as plastic. For example, an unprecedented flexible device can be created. It becomes possible.

  In the case of using a low molecular weight material as the organic semiconductor material, the organic semiconductor film can be formed in a desired region by a vacuum deposition method using a shadow mask or a structure with a reverse taper shape.

  In addition, a technique for forming an organic semiconductor film in a desired region by using a plurality of self-assembled monolayers with different contact angles as a template and separately coating a low molecular organic semiconductor material has been proposed (non-patent document). Reference 1). This technique is highly convenient because there is no need to form a structure such as a bank that defines the film forming portion, and there is no hindrance to miniaturization by the bank.

Patterned Growth of Large Oriented Organic Semiconductor Single Crystals on Self-Assenmbled Monolayer Templates, Alejandro L. Briseno et.al., J. Am. Chem. Soc., 2005, 127 (35), 12164-12165

When a polymer material is used as the organic semiconductor material, film formation by vacuum deposition is impossible, and film formation by various printing methods is generally performed.
However, since it is difficult to miniaturize by the conventional printing method, and the current normal printing technology tends to cause displacement, it is applied only to the film forming part after forming a structure such as a bank for defining the film forming part. There was a need, and further miniaturization was inhibited.

  Further, in the technique of Non-Patent Document 1 described above, fine coating can be performed by miniaturizing the self-assembled monolayer, but when a polymer material is used as a semiconductor material, the length and molecular weight of the molecule. Is larger than that of low molecular weight materials, the fluidity is low, and it is impossible to separate the paint along the template.

  The present invention has been made in view of the above-described problems, and an object of the present invention is to provide a method for manufacturing a semiconductor device that enables separate coating using a template even if the semiconductor material has a high molecular weight. is there.

  The invention according to claim 1, which has been made to solve the above-described problem, is a method for manufacturing a semiconductor device including a substrate on which an organic semiconductor film is formed in a predetermined region, and the manufacturing method includes a covering step. And a removing step.

  The coating step includes a second self-assembly in which a contact angle between the first region where the first self-assembled monolayer is formed and a predetermined solvent is smaller than that of the first self-assembled monolayer. A step of coating the substrate with a solution made of the solvent and the organic semiconductor material in a state where the substrate having the second region where the monomolecular film is formed is at a predetermined temperature or higher.

Moreover, a removal process is a process of removing the said solution which coat | covered the said 1st area | region.
In such a method for manufacturing a semiconductor device, the first region and the second region of the solution are separately applied due to the substrate being at a predetermined temperature or higher. Therefore, after the removal step, the solution is in a state of covering the second region.

As described above, according to the above manufacturing method, even when the organic semiconductor material has a high molecular weight, it is possible to separately coat the first region and the second region as a template.
As a result, a semiconductor device in which an organic semiconductor film is formed in the second region can be manufactured regardless of the molecular weight of the organic semiconductor material.

  In addition, since the size of the organic semiconductor film is determined by the size of the second region, the size of the organic semiconductor film can be changed by changing the size of the second region. Therefore, by forming the second region finely, it becomes possible to form a film finer than the conventional printing method.

Further, a structure such as a bank for defining the film forming portion is not necessary, and the obstruction of the miniaturization by them is eliminated, so that the film can be easily miniaturized.
The self-assembled monomolecular film means a monomolecular film that is formed autonomously by adsorbing organic molecules on the solid surface by immersing the solid in a solution of organic molecules.

The invention according to claim 2 is the method for manufacturing a semiconductor device according to claim 1, wherein the organic semiconductor material is a polymer organic semiconductor material.
With such a manufacturing method of a semiconductor device, even with a polymer organic semiconductor material, it is possible to appropriately perform coating along the template.

  In addition, compared with a low molecular organic semiconductor material, a high molecular organic semiconductor material has an advantage that it is easily formed into a solution using an organic solvent and is suitable for a coating process. Since printing processes such as inkjet and rotary press can be applied, cost reduction and size increase (large screen, etc.) become easy.

The invention described in claim 3 is the method of manufacturing a semiconductor device according to claim 1 or 2, wherein the covering step is a step of immersing the substrate in a solution.
With such a method of manufacturing a semiconductor device, the solution coating on the second region can be easily realized.

  Invention of Claim 4 is a manufacturing method of the semiconductor device of Claim 1 or Claim 2, Comprising: A coating process is a dip coat method, a drop cast method, a spray coating method, screen printing, gravure printing, It is a step of coating a substrate with a solution using one or more methods selected from the group of flexographic printing and inkjet printing.

With such a method of manufacturing a semiconductor device, the solution coating on the second region can be easily realized.
According to a fifth aspect of the present invention, in the method for manufacturing a semiconductor device according to any one of the first to fourth aspects, the temperature of the solution in the covering step is equal to or higher than the predetermined temperature.

  With such a method for manufacturing a semiconductor device, it is possible to prevent the temperature of the substrate from being lowered when the substrate touches the solution, so that it is possible to prevent the color separation along the template from being disabled.

According to a sixth aspect of the present invention, in the method for manufacturing a semiconductor device according to any one of the first to fifth aspects, the temperature of the substrate in the covering step is 30 ° C. or higher.
With such a method of manufacturing a semiconductor device, it is possible to perform coating along the template with high accuracy. In addition, if the temperature of a board | substrate shall be below the boiling point of a solution, boiling of the solution at the time of a solution contacting a board | substrate will be suppressed.

  By the way, the specific method for removing the solution which coat | covered the 1st area | region in the removal process mentioned above is not specifically limited. For example, air blow or suction can be considered. In addition, the method described in claim 7 may be used.

  According to a seventh aspect of the present invention, in the method for manufacturing a semiconductor device according to any one of the first to sixth aspects, the removing step inclines at least the first region of the substrate with respect to the horizontal plane. It is a process to make it feature.

  With such a method for manufacturing a semiconductor device, the solution covering the first region can be removed from the first region by utilizing the fact that the solution moving due to its own weight. This removal step may be performed in combination with other removal methods.

According to an eighth aspect of the present invention, in the method for manufacturing a semiconductor device according to the seventh aspect, the inclination angle of the first region with respect to the horizontal plane in the removing step is 20 ° or more.
With such a method for manufacturing a semiconductor device, the solution can easily move from the first region, so that the solution can be smoothly removed from the first region.

  The invention according to claim 9 has the following characteristics in the method of manufacturing a semiconductor device according to claim 7. First, in the removing step, the inclination angle of the first region with respect to the horizontal plane is 30 ° or more. Further, the predetermined temperature is a temperature of 40 ° C. or higher and the boiling point of the solvent or lower. And X + Y ≧ 120 is satisfied when the predetermined temperature is X ° C. and the inclination angle is Y °.

With such a method for manufacturing a semiconductor device, the temperature and inclination angle of the substrate are included in an appropriate range, so that the solution can be smoothly removed from the first region.
According to a tenth aspect of the present invention, in the method of manufacturing a semiconductor device according to any one of the first to ninth aspects, the semiconductor device is a thin film transistor, and the organic semiconductor film is a channel portion in the thin film transistor. It is characterized by that.

  With such a method for manufacturing a semiconductor device, the channel portion of the thin film transistor can be formed by using the method for manufacturing a semiconductor device according to any one of claims 1 to 9 described above.

  The invention according to claim 11 is the method of manufacturing a semiconductor device according to any one of claims 1 to 9, wherein the semiconductor device is an organic electroluminescence element, and the organic semiconductor film is organic electroluminescence. It is a layer in contact with the transparent electrode in the element.

  If it is the manufacturing method of such a semiconductor device, the layer which contact | connects the transparent electrode of an organic electroluminescent element will be formed using the manufacturing method of the semiconductor device of any one of Claim 1-9 mentioned above. can do.

Note that the layer in contact with the transparent electrode corresponds to a hole injection layer in an organic electroluminescence element, an insulating layer for defining a light emitting pixel, or the like.
The invention according to claim 12 is the method for manufacturing a semiconductor device according to any one of claims 1 to 9, wherein the semiconductor device is a solar cell, and the organic semiconductor film is a transparent electrode in the solar cell. It is a layer which touches.

  If it is the manufacturing method of such a semiconductor device, the layer which contacts the transparent electrode of a solar cell will be formed using the manufacturing method of the semiconductor device of any one of Claim 1 to Claim 9 mentioned above. Can do.

Sectional views and top views showing a manufacturing process of the thin film transistor in Embodiment 1. Sectional views and top views showing a manufacturing process of the thin film transistor in Embodiment 1. Sectional views and top views showing a manufacturing process of the thin film transistor in Embodiment 1. Schematic of patterning of self-assembled monolayer in Example 1 Sectional views and top views showing a manufacturing process of the thin film transistor in Embodiment 1. Schematic of dip coating method in Example 1 Sectional view and top view of the thin film transistor manufactured in Example 1 Sectional drawing and top view showing the thin film transistor manufactured in Example 2 Schematic diagram of dip coating method in Example 3 Schematic of the drop cast method in Example 6 The figure which shows the thin-film transistor of a modification Sectional drawing which shows the preparation process of the organic electroluminescent element in Example 9 Schematic of patterning of self-assembled monolayer in Example 9 Sectional drawing and top view which show the organic electroluminescent element produced in Example 9

Embodiments of the present invention will be described below with reference to the drawings.
[Production of Thin Film Transistor]

In this example, a thin film transistor having a channel portion in which a film formation region of a polymer organic semiconductor film was defined by a self-assembled monomolecular film was manufactured by the following steps 1 to 6.
(Process 1)
An N-type silicon (Si) wafer was used as the substrate 1, and a 250 nm silicon oxide (SiO ₂ ) film (gate insulating film 2) was formed on the surface by thermal oxidation, followed by cleaning.

Subsequently, 5 nm thick chromium (Cr) 3a and 50 nm thick gold (Au) 3b were continuously formed on the gate insulating film 2 by resistance heating vacuum deposition.
A sectional view and a top view of the substrate 1 in this state are shown in FIGS. FIG. 1A is an AA cross section of FIG. Note that the cross-sectional view and the top view schematically show the substrate 1 and there are inaccurate portions such as the thickness ratio. The same applies to the following drawings.
(Process 2)
Photoresist mainly composed of novolak resin was applied to the film-forming surface of step 1. After that, a photoresist pattern is formed by exposure and development using a photomask so that a desired pattern can be obtained, and gold (Au) is etched using a dedicated etching solution containing gold (Au) potassium iodide and iodine. Similarly, chromium (Cr) was etched using a dedicated etchant mainly composed of nitric acid. Thereafter, the resist film was stripped using a dedicated resist stripping solution.

Thus, the source electrode 3c and the drain electrode 3d formed by laminating chromium (Cr) 3a and gold (Au) 3b were formed. 2A and 2B are a cross-sectional view and a top view of the substrate 1 in this state. In the following drawings, only the source electrode 3c and the drain electrode 3d are shown for convenience, and the laminated structure of chromium (Cr) 3a and gold (Au) 3b is not clearly shown.
(Process 3)
The surface of the substrate 1 was cleaned using an ozone treatment apparatus. At this time, the contact angle of the surface of the substrate 1 with respect to water was 3 ° or less.

Subsequently, the substrate 1 is immersed in a solution in which the perfluorochlorosilane compound CF ₃ (CF ₂ ) ₅ CH ₂ SiCl ₃ is dispersed in toluene, and a first self-assembled monolayer film having a perfluoroalkyl group (first SAM) A film 5) was formed on the surface of the substrate 1.

3A and 3B are a sectional view and a top view of the substrate 1 in this state. As shown in FIG. 3B, the first SAM film 5 is formed on the gate insulating film 2. Specifically, a hydroxyl group (—OH) on the surface of the gate insulating film 2 and a perfluorochlorosilane compound are bonded to each other, and a perfluorosilane group (CF ₃ (CF ₂ ) ₅ CH is bonded to the surface of the substrate 1 (the surface of the gate insulating film 2). ₂ Si-) film is formed and becomes liquid repellent. At this time, the contact angle with respect to water of the surface of the substrate 1 (the surface of the first SAM film 5) was 113 °, and similarly, the contact angle with respect to dichlorobenzene was 83.4 °.
(Process 4)
The region 5a to be coated with the polymer organic semiconductor film in the first SAM film 5 was deleted by applying ozone treatment with the metal mask 7 in close contact with the substrate 1 as shown in FIG.
(Process 5)
A substrate 1 is immersed in a solution in which a phenethylsilane compound (β-phen: C ₆ H ₅ (CH ₂ ) ₂ SiCl ₃ ) is dispersed in toluene, and a second self-assembled monolayer having a phenethyl group (second SAM) A film 6) was formed in region 5a. A cross-sectional view and a top view of the substrate 1 in this state are shown in FIGS.

At this time, the contact angle with respect to water of the surface of the second SAM film 6 was 84.4 °, and similarly the contact angle with dichlorobenzene was 6.0 °, which showed higher lyophilicity than the region where the first SAM film 5 was formed.
(Step 6)
As shown in FIG. 6, the dip coating method was performed using a poly (3-hexylthiophene) (P3HT) 0.5 weight percent dichlorobenzene solution 8 having a molecular weight Mw = 34,000. Here, the substrate 1 was heated to 40 ° C. in advance, and the substrate 1 was immersed in the solution 8 temperature-controlled at 40 ° C. to coat the substrate 1 with the solution 8 (a coating step in the present invention). Thereafter, the substrate 1 was pulled up vertically, and the solution 8 covering the region where the first SAM film 5 was formed on the substrate 1 was removed (removal step in the present invention).

  As a result, the polymer organic semiconductor film 4 was successfully obtained in a desired region on the substrate 1 (region where the second SAM film 6 was formed). 7A and 7B are a cross-sectional view and a top view of the thin film transistor manufactured as described above.

When the thin film transistor manufactured as described above was operated as a P-type transistor having an N-type silicon (Si) wafer (substrate 1) as a gate electrode and a polymer organic semiconductor film 4 as an active layer, mobility It was 1 × 10 ⁻³ cm ² / V / sec.

As a comparative example, after step 2, a polymer organic semiconductor film was formed by a spin coating method, and unnecessary portions of the polymer organic semiconductor film were removed to produce a thin film transistor. The mobility of this thin film transistor was 0.89 × 10 ⁻³ cm ² / V / sec.

  When the film is formed by using a spin coat method or the like and the unnecessary portion of the polymer semiconductor film is removed, the removed portion of the polymer organic semiconductor material is wasted, but in this embodiment, only the second SAM film 6 is formed. Since the film is formed, there is no waste of material.

In this example, the timing for forming the source electrode 3 c and the drain electrode 3 d was changed from the manufacturing method of Example 1 after the polymer organic semiconductor film 4 was formed.
Specifically, after forming the gate insulating film 2 (silicon oxide (SiO ₂ ) film) on the substrate 1 in the above step 1, the same steps up to step 6 are performed without performing the step of forming chromium and gold and the step 2. It was prepared. Next, gold was deposited in a predetermined region by a vacuum deposition method using a shadow mask to form a source electrode 3c and a drain electrode 3d.

8A and 8B are a cross-sectional view and a top view of the manufactured thin film transistor. When this thin film transistor was operated as a P-type transistor in the same manner as in Example 1, the mobility was 4 × 10 ⁻³ cm ² / V / sec.

As a comparative example, after forming the gate insulating film 2 on the substrate 1 in the above step 1, a polymer organic semiconductor film is formed by spin coating, and then gold is deposited by vacuum deposition using a shadow mask. A thin film transistor was formed by forming a film in a predetermined region and using the source electrode 3c and the drain electrode 3d. The mobility of this thin film transistor was 1.4 × 10 ⁻³ cm ² / V / sec.

In this example, thin film transistors were manufactured by changing the film forming conditions of the polymer organic semiconductor film 4.
As shown in FIG. 9, the substrate 1 subjected to the same steps as in Example 1 and Step 5 is subjected to a dip coating method in Step 6 using a 0.75 weight percent dichlorobenzene solution 8a of P3HT having a molecular weight Mw = 34,000. Carried out. At this time, the temperature of the substrate 1 was set to 30 ° C., 40 ° C., 60 ° C., 80 ° C., or 100 ° C. In addition, the angle at which the substrate 1 was pulled up (inclination angle with respect to the horizontal plane) was set to any of 10 °, 20 °, 30 °, 40 °, 60 °, 80 °, and 90 °. The temperature of the solution 8 a was set to be the same as the temperature of the substrate 1.

Table 1 shows the results of forming the polymer organic semiconductor film 4 in the region where the second SAM film 6 was formed. The criteria for determining the film formation result are as follows.
Good: Partially the same pattern as that of the metal mask 7 is not possible: Partially the polymer organic semiconductor film 4 is not formed on the first SAM film 5: In a certain part on the substrate 1, The polymer organic semiconductor film 4 is formed on the 1 SAM film 5, and the polymer organic semiconductor film 4 and the continuous film are formed on the second SAM film 6. As a reference example, the temperature of the substrate 1 is 20 ° C. The film formation results when the inclination angle is 0 ° and 5 ° are also shown.

When the tilt angle is 10 °, the film can be formed only when the substrate temperature is 100 ° C. or higher. When the tilt angle is 20 ° or higher, the film can be formed in a wide temperature range. However, in order to form a film satisfactorily, it is desired to be 30 ° or more.

Film formation is possible when the substrate temperature is 30 ° C. or higher, but it is desirable that the substrate temperature be 40 ° C. or higher for good film formation.
In particular, when the tilt angle is 30 ° or more, the substrate temperature is 40 ° C., the substrate temperature is X ° C., and the tilt angle is Y °, X + Y ≧ 120 is satisfied. It was possible to form a film.

In this example, the second SAM film 6 was formed using a material different from that in Example 1, and the thin film transistor was manufactured by changing the film forming conditions of the polymer organic semiconductor film 4.
Substrate 1 that has undergone the same steps as in Example 1 and Step 4 above is a solution in which aminopropylsilane compound NH ₂ (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ (APTES) is dispersed in toluene in Step 5. A second self-assembled monomolecular film (second SAM film 6) having an amino group was formed in the region 5a. At this time, the contact angle with water on the surface of the second SAM film 6 was 33 °, and similarly the contact angle with dichlorobenzene was 7.1 °.

  Then, the board | substrate 1 was immersed in the said solution by the dip coating method similarly to the process 6 of Example 1. FIG. Here, the temperature of the substrate 1 was set to 30 ° C., 60 ° C., 80 ° C., 100 ° C., or 120 ° C. Further, the inclination angle of the substrate 1 was set to any of 10 °, 20 °, 30 °, 40 °, 60 °, 80 °, and 90 °. The temperature of the solution was set to be the same as the temperature of the substrate 1.

  Table 2 shows the results of film formation of the polymer organic semiconductor film 4. As a reference example, the results of film formation when the temperature of the substrate 1 is 20 ° C. and when the inclination angles are 0 ° and 5 ° are also shown.

When the tilt angle was 10 °, film formation was possible only when the substrate temperature was 80 ° C. or higher. In order to form a film satisfactorily, it is desired to be 30 ° or more.

Film formation is possible when the substrate temperature is 30 ° C. or higher, but it is desirable that the substrate temperature be 60 ° C. or higher for good film formation.
In particular, when the tilt angle was 40 ° or more and the substrate temperature was 60 ° C., the polymer organic semiconductor film 4 could be satisfactorily formed.

  In this example, the concentration of the polymer semiconductor material in the APTES toluene solution was changed from the manufacturing method of Example 4 above, and the film forming conditions of the polymer organic semiconductor film 4 were changed. Was formed.

  The temperature of the substrate 1 was set to 60 ° C., 90 ° C., or 120 ° C. The inclination angle of the substrate 1 was set to 20 °, 40 °, or 60 °. The temperature of the solution was set to be the same as the temperature of the substrate 1. Three patterns of 0.15, 0.75, and 1.5 weight percent were prepared for the solution concentration. The film formation results for each concentration are shown in Tables 3 to 5. As a reference example, a film formation result when the temperature of the substrate 1 is 30 ° C. is also shown.

When the solution concentration was high (1.5 weight percent), even if the inclination angle of the substrate 1 was small, the film could be satisfactorily formed in a wide range except for the substrate temperature of 30 ° C. or less.

  On the other hand, when the solution concentration is low (0.15 weight percent), the film forming performance is degraded when the tilt angle is 20 °. However, when the tilt angle is 40 ° or more, part of the film temperature is 30 ° C. Could be formed into a film.

  At any concentration, the film could be satisfactorily formed at least when the substrate tilt angle was 40 ° or more and the substrate temperature was 60 ° C. or more.

In this example, a thin film transistor was manufactured by using the drop cast method for forming the polymer organic semiconductor film 4.
As shown in FIG. 10, the substrate 1 that has undergone the same steps up to Example 1 and Step 5 is heated to an arbitrary temperature in Step 6 and tilted so that the tilt angle is 40 °. A 0.75 weight percent dichlorobenzene solution 11 of P3HT with Mw = 34,000 was dropped (coating step in the present invention). Of the solution 11 dropped on the substrate 1, the solution 11 covering the region where the first SAM film 5 was formed was removed by flowing down due to the inclination of the substrate 1 (removal step in the present invention). In this way, the polymer organic semiconductor film 4 was formed in a desired region on the substrate 1 (region where the second SAM film 6 was formed).

The substrate temperature was set to 30 ° C., 40 ° C., 60 ° C., 80 ° C., or 100 ° C. The temperature of the solution was 25 ° C.
Table 6 shows the film formation results. As a reference example, a film formation result when the temperature of the substrate 1 is 20 ° C. is also shown.

As can be seen from Table 6, even when the drop cast method was used, a film could be formed in the same manner as when the dip coating method was used. In particular, the results were better than those of the dip coating method at 30 ° C. and 40 ° C.

In this example, the polymer organic semiconductor film 4 was formed by arbitrarily changing the molecular weight of P3HT from the manufacturing method of Example 6.
Three patterns of molecular weight of P3HT were prepared: 21100, 34000, and 94052. The substrate temperature was 40 ° C. and the substrate tilt angle was 40 °. Table 7 shows the film formation results. As a reference example, the result of film formation in the case of molecular weight 128800 is also shown.

As can be seen from Table 7, a polymer organic semiconductor film can be formed if the molecular weight is 100000 or less. In particular, when the molecular weight is 40000 or less, the film can be satisfactorily formed.

In this example, the polymer organic semiconductor film 4 was formed by changing the self-assembled monolayer material of the first SAM film 5 and the second SAM film 6 from the manufacturing method of Example 1.
Table 8 shows the results of film formation. In the table, A is the material of the first SAM film 5, and B is the material of the second SAM film 6. The angle in parentheses is the contact angle for dichlorobenzene. Abbreviations in the table are described below.
・ Β-Phen phenethyltrichlorosilane ・ APTES 3-aminopropyltriethoxysilane ・ PTES propyltriethoxysilane ・ FPTS (3,3,3-trifluoropropyl) trimethoxysilane ・ FOTS (1H, 1H, 2H, 2H- Perfluorooctyl) trichlorosilane

As can be seen from Table 8, the larger the difference between the contact angles of A and B, the better. Film formation becomes possible when the difference in contact angle exceeds 38 °, and film formation is particularly good when the difference exceeds 70 °.
[Effects of Invention on Fabrication of Thin Film Transistor]
As described in Examples 1 to 8, a high-molecular-weight organic semiconductor is produced by using the method for manufacturing a semiconductor device of the present invention for manufacturing a thin film transistor. The first SAM film 5 and the second SAM film 6 of the solution containing the material can be separately applied as templates.

As a result, even if the semiconductor material is a polymer organic semiconductor material, a thin film transistor in which the polymer organic semiconductor film 4 is formed on the second SAM film 6 can be manufactured.
In addition, since the size of the polymer organic semiconductor film 4 is determined by the size of the second SAM film 6, the size of the polymer organic semiconductor film 4 can be changed by changing the size of the second SAM film 6. Therefore, by forming the second SAM film 6 finely, it becomes possible to form a film finer than the conventional printing method.

Further, a structure such as a bank for defining the film forming portion is not necessary, and the obstruction of the miniaturization by them is eliminated, so that the film can be easily miniaturized.
In addition, by preheating the solution containing the semiconductor material, it is possible to prevent the temperature of the substrate 1 from being lowered when the substrate 1 touches the solution. It can be prevented from disappearing.

Further, by using the dip coating method and the drop cast method, the coating of the solution on the second SAM film 6 and the removal from the first SAM film 5 can be realized at the same time, and the film forming operation can be simplified. .
[Modifications for Fabrication of Thin Film Transistor]
As mentioned above, although the Example regarding manufacture of the thin-film transistor of this invention was described, this invention is not limited to the said Example at all, As long as it belongs to the technical scope of this invention, it can be taken as various forms. Nor.

  For example, although an example in which an N-type silicon (Si) wafer is used as the substrate 1 is illustrated, the material of the substrate 1 is not particularly limited, and can be appropriately determined depending on the material of each layer to be laminated. For example, a semiconductor material such as a Si wafer highly doped with boron (B) phosphorus (P) or the like, a metal foil such as Al, a material made of various materials such as glass, quartz, or resin can be used.

When a highly flexible material such as resin is used for the substrate, the inclination angle of the first SAM film portion corresponds to the inclination angle of the substrate of each of the above embodiments.
Further, as electrode materials of the gate electrode (corresponding to the substrate 1), the source electrode 3c and the drain electrode 3d, besides the structures of the above embodiments, highly doped silicon, Ti, Al, Cr, Mo, W, Ta, Cu Ni, Ag, Au, Pt, Pd and other metals or alloys thereof can be used. Alternatively, a conductive polymer such as polyaniline or PEDOT: PSS can be used. Or, any of oxide transparent conductive thin films such as indium tin-oxide (ITO), indium-zinc oxide (IZO), indium oxide (In ₂ O ₃ ), zinc oxide (ZnO), tin oxide (SnO ₂ ) The main composition can be used. The thickness of each electrode is preferably about 10 to 500 nm.

Moreover, although the silicon oxide (SiO ₂ ) film is exemplified as the gate insulating film 2, the gate insulating film material is not limited to this, and inorganic oxide thin films of various insulating materials represented by SiO ₂ and Al ₂ O _3. An inorganic nitride film such as Si ₃ N ₄ or an organic thin film can be used, but an inorganic oxide thin film having a high relative dielectric constant is particularly preferable.

  Inorganic oxides include silicon oxide, aluminum oxide, tantalum oxide, titanium oxide, vanadium oxide, barium strontium titanate, barium zirconate titanate, lead zirconate titanate, lead lanthanum titanate, strontium titanate, barium titanate , Yttrium oxide and the like, but not limited thereto. Of these, silicon oxide, aluminum oxide, tantalum oxide, and titanium oxide are preferable.

Similarly, examples of the inorganic nitride film include silicon nitride and aluminum nitride. Also, a laminated film of an inorganic nitride thin film and an inorganic oxide thin film can be suitably used.
Examples of the organic thin film include polyimide, polyamide, polyester, polyacrylate, photo-curing polymer of photo radical polymerization system, photo cation polymerization system, copolymer containing acrylonitrile component, polyvinyl phenol, polyvinyl alcohol, novolac resin, It is also possible to use phosphazene compounds including ethyl pullulan, polymer, and elastomer. Similarly, a laminated film of the organic thin film and the inorganic oxide thin film can also be used.

  The thickness of the gate insulating thin film is preferably about 10 to 500 nm, but a natural oxide film and a self-assembled monolayer for defining the film forming region may be used as the gate insulating film, in which case the gate insulating film thickness is 3 nm or less. sell.

  Moreover, although P3HT was illustrated as a polymeric organic-semiconductor material, a polymeric organic-semiconductor material is not limited to this. For example, a material of polythiophene, polyphenylene vinylene, or polyfluorene that is a π-electron conjugated polymer can be used as the polymer organic semiconductor material.

  Specifically, as a p-type polymer organic semiconductor, poly (3-octylthiophene), poly (3-hexylthiophene), poly (3-dodecylthiophene), poly (3,3 ′ ″ didodecylorthothiophene), Polythiophenethiophene-thiophene copolymers, polythiophene derivatives, poly (p-phenylene-vinylene), poly (2-methoxy-5- (2-ethyl-hexyloxy) -1,4-phenylenevinylene), poly ( 2-methoxy-5- (3 ′, 7′-dimethyl-octyloxy) -1,4-phenylenevinylene), poly (2-butyl, 5- (2′-ethylhexyl) -1,4-phenylenevinylene), etc. The polyphenylene vinylene derivative is preferable. Other examples include, but are not limited to, polyvinylcarbazole, polytriphenylamine derivatives, polyfluorene-thiophene copolymers, polyfluorene-benzothiazole copolymers, and the like.

  Examples of the n-type organic polymer semiconductor include, but are not limited to, polypyridine, polyquinoline, derivatives thereof, poly (benzobisimidazobenzophenanthroline), and polybenzophenanthroline derivatives.

Note that a material having a low molecular weight may be used as the organic semiconductor material. For example, a soluble pentacene precursor, a soluble tetrabenzoporphyrin precursor, 6,13-triisopropylpurityethynylpentacene and its analogs, benzothieno [3,2-b] benzothiophene derivatives, quarterthiophene derivatives, fullerenes (C ₆₀ ) And derivatives thereof, but are not limited thereto.

  In each of the above embodiments, a self-assembled monomolecular film (first SAM film 5) in a region where the polymer organic semiconductor film 4 is not desired to be formed is formed first, and the polymer organic semiconductor film 4 is manufactured later. Although the configuration in which the self-assembled monolayer film (second SAM film 6) in the region desired to be formed is illustrated, the order of forming the self-assembled monolayer film may be reversed.

  In each of the above-described embodiments, the film-forming region of the polymer organic semiconductor film 4 is defined using the self-assembled monomolecular films (first SAM film 5 and second SAM film 6) formed on the gate insulating film 2. However, as shown in FIG. 11, after the self-assembled monomolecular film (first SAM film 5 and second SAM film 6) is formed on the substrate 1 to form the polymer organic semiconductor film 4, the source electrode 3c is formed. The drain electrode 3d and the gate insulating film 2 may be formed to form the gate electrode 12.

Further, in each of the above embodiments, the configuration in which the organic semiconductor material solution is coated on the surface of the substrate 1 (the surface of the second SAM film 6) by using the dip coating method or the drop cast method is exemplified. The above-mentioned solution may be coated on the substrate 1 using a technique such as gravure printing, flexographic printing, or inkjet printing.
[Production of organic electroluminescence element]

In this example, an organic electroluminescence device (hereinafter referred to as organic electroluminescence device) in which the film-forming region of the polymer organic hole injection layer is defined by the self-assembled monolayer formed on the anode by the following steps 1 to 6. EL device).
(Process 1)
A glass substrate provided with an indium-tin oxide film (ITO film 22) was used as the substrate 21, and the surface of the substrate 21 (ITO film 22 surface) was cleaned using an ozone treatment apparatus. At this time, the contact angle of the ITO film 22 surface with water was 8 ° or less.
(Process 2)
A substrate 21 is immersed in a solution in which a perfluorochlorosilane compound CF ₃ (CF ₂ ) ₅ CH ₂ SiCl ₃ is dispersed in toluene, and a first self-assembled monomolecular film having a perfluoroalkyl group (first SAM film 28). Was formed on the surface of the ITO film 22. A cross-sectional view of the substrate 21 in this state is shown in FIG. At this time, the contact angle of water on the surface was 113 °.
(Process 3)
The first SAM film 28 on the region 22a to be coated with the polymer hole injection layer material on the surface of the ITO film 22 is formed using a photomask 30 patterned so that the region 22a is not shielded as shown in FIG. The substrate was exposed to ultraviolet light having a wavelength of 172 nm or 254 nm in close contact with the substrate 21 to remove oxygen molecules between the substrate 21 and the photomask 30 by radicalization. A cross-sectional view of the substrate 21 in this state is shown in FIG.
(Process 4)
A substrate 21 is immersed in a solution in which an aminopropylsilane compound NH ₂ (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ (APTES) is dispersed in toluene, and a second self-assembled monolayer having an amino group ( A second SAM film 29) was formed in the region 22a. A sectional view of the substrate 21 in this state is shown in FIG.

At this time, the contact angle of the surface of the second SAM film 29 with respect to water was 28 °.
(Process 5)
Similarly to the drop casting method of Example 6 shown in FIG. 10, the substrate 21 is heated to 30 ° C. and inclined so that the inclination angle becomes 40 °, and from the syringe 10, poly (3 , 4-Ethylenedioxythiophene) / polystyrene sulfonic acid (PEDOT / PSS) aqueous solution 11a (Clevios P Al 4083 manufactured by HCstarck). An injection layer 23 was formed.

A sectional view of the substrate 21 in this state is shown in FIG.
(Step 6)
A hole transport layer 24 was formed on the hole injection layer 23 by a vacuum resistance heating vapor deposition method using a shadow mask. Moreover, the organic light emitting layer 25 was formed on the hole transport layer 24 by the same film forming method. Diphenylnaphthyldiamine (α-NPD) was used as the hole transport layer material, and tris (8-quinolinolato) aluminum (Alq3) was used as the light emitting layer material. At this time, the film thicknesses of α-NPD and Alq3 were 40 nm and 60 nm, respectively.

  Subsequently, 1 nm of lithium fluoride (LiF) is deposited on the organic light emitting layer 25 as the electron injection layer 26, and aluminum (Al) that becomes the cathode layer 27 is formed on the organic light emitting layer 25 using a shadow mask different from the conventional one. Was deposited to a thickness of 100 nm. FIGS. 14A and 14B show a cross-sectional view and a top view of the organic EL element fabricated as described above. FIG. 14A is a cross-sectional view taken along line BB in FIG.

  In the organic EL device manufactured as described above, when a voltage of 4 V is applied between the ITO film 22 (anode) and the cathode layer 27, a current of 0.52 mA flows, and polymer hole injection on the substrate 21 is performed. Light emission in the region where the layer 23 was formed was confirmed.

  As a comparative example, an organic EL element was produced in the same process as in this example except that a bank for inkjet printing was formed first and a PEDOT / PSS aqueous solution was printed by inkjet printing. When the drive storage life at 80 ° C. was measured, the organic EL device of this example maintained light emission for a long time with less expansion of the non-light emitting region.

In this example, an organic EL element in which an insulating layer for defining a luminescent pixel was defined by a self-assembled monomolecular film was produced.
Here, the process 2 and the process 4 were changed from the manufacturing method of Example 9, and the process was added after the process 4. FIG.

In step 2, a phenethylsilane compound C ₆ H ₅ (CH ₂ ) ₂ SiCl ₃ (β-phen) was used for the first self-assembled monolayer instead of the perfluorochlorosilane compound.
In Step 4, a perfluorochlorosilane compound CF ₃ (CF ₂ ) ₅ CH ₂ SiCl ₃ was used for the second self-assembled monolayer instead of the aminopropylsilane compound.

  Next, a polyvinylphenol (PVP) 10 weight percent concentration toluene solution was used as an insulating layer for defining light emitting pixels, and a PVP film was formed in a desired region (on the first SAM film 28) by a dip coating method. Here, the substrate 21 was heated to 50 ° C. in advance, the substrate 21 was immersed in a solution whose temperature was controlled at 50 ° C., and pulled up vertically.

Thereafter, it was produced in the same manner as in Steps 5 and 6 of Example 9. The polymer hole injection layer 23 was formed on the second SAM film 29 and the PVP film.
In the organic EL device produced as described above, when a voltage of 5 V was applied between the ITO film 22 (anode) and the cathode layer 27, light emission was confirmed in a region where no PVP film was formed. The current value at this time was 0.13 mA.
[Effect of invention relating to fabrication of organic electroluminescence element]
As described in Examples 9 and 10, by using the method for manufacturing a semiconductor device of the present invention for manufacturing an organic electroluminescence element, the same operations and effects as those for manufacturing the above-described thin film transistor can be obtained.
[Variation of production of organic electroluminescence element]
As mentioned above, although the Example regarding organic EL element preparation of this invention was described, this invention is not limited to the said Example at all, and as long as it belongs to the technical scope of this invention, it can take various forms. Needless to say.

  For example, the substrate 21 is exemplified by a configuration using a glass substrate provided with an indium-tin oxide film (ITO film 22). However, the material of the substrate 21 is not limited to the above-described configuration, and the material of each layer to be stacked is used. It can be determined as appropriate.

  For example, it can be selected from a semiconductor material such as a Si wafer, a metal such as Al, various materials such as glass, quartz, or a resin from a flexible material or a hard material according to the application. Specific examples include substrates made of materials such as glass, quartz, polyethylene, polypropylene, polyethylene terephthalate, polymethacrylate, polymethyl methacrylate, polymethyl acrylate, polyester, and polycarbonate. The shape of the substrate 21 may be a single wafer shape or a continuous shape. Specific examples of the shape include a card shape, a film shape, a disk shape, and a chip shape.

Moreover, as an anode (ITO film | membrane 22) material and cathode layer 27 material, besides the structure of said each Example, highly doped silicon, Ti, Al, Cr, Mo, W, Ta, Cu, Ni, Ag, Au, Examples thereof include metals such as Pt and Pd or alloys thereof, but are not limited thereto. In particular, as the anode material, transparent conductive films such as indium tin oxide (ITO), indium zinc oxide (IZO), indium oxide (In ₂ O ₃ ), zinc oxide (ZnO), tin oxide (SnO ₂ ), gold A metal having a large work function such as platinum is preferred. Similarly, a metal material having a small work function such as aluminum (Al), magnesium (Mg), silver (Ag) is preferably used as the cathode material.

  In addition, poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid (PEDOT / PSS) is exemplified as the material of the polymer hole injection layer 23, but other materials such as polyaniline, polypyrrole, polythiophene, etc. However, the present invention is not limited to this.

  Moreover, although the diphenyl naphthyl diamine ((alpha) -NPD) was illustrated as a material of the positive hole transport layer 24, a positive hole transport layer material is not limited to this. Examples thereof include triphenylamine materials such as triphenyldiamine (TPD) and starburst-like amines (for example, m-MTDATA, o-, m-PTDATA, p-PMTDATA). In addition, phthalocyanine, naphthalocyanine, porphyrin, oxadiazole, triazole, imidazole, imidazolone, pyrazoline, tetrahydroimidazole, hydrazone, stilbene, pentacene, polythiophene, butadiene, or a derivative thereof can be used. The hole transport layer 24 may be a single layer, or may be composed of a mixture of the above materials or a plurality of layers as necessary.

The organic light emitting layer 25 may contain a fluorescent material or a phosphorescent material which is a compound having a light emitting function. In particular, those containing a phosphorescent substance in the organic light emitting layer are excellent in luminous efficiency.
Examples of fluorescent substances include coumarin derivatives (coumarin 6) incorporated in tris (8-quinolinolato) aluminum (Alq3). Examples of such a fluorescent substance include at least one selected from compounds such as quinacridone, rubrene, and styryl dyes. Examples of phosphorescent substances include organic iridium complexes and organic platinum complexes. Examples of the polymer light emitting material include polyphenylene vinylene derivatives, polythiophene derivatives, polyacetylene derivatives, polyvinyl carbazole, polyfluorenone derivatives, polyfluorene derivatives, polyquinoxaline derivatives, and copolymers thereof.

  Moreover, although lithium fluoride (LiF) was illustrated as the electron injection layer 26, the electron injection layer 26 is not limited to this, and lithium oxide, strontium, magnesium oxide, magnesium fluoride, strontium fluoride, calcium fluoride, Alkali metals, alkali metal halides, alkali metal organic complexes, and the like such as barium fluoride, barium oxide, aluminum oxide, strontium oxide, calcium, lithium, cesium, and cesium fluoride can be used.

  Although not shown, one or more electron transport layers may be provided between the organic light emitting layer 25 and the cathode layer 27. For example, as a material for forming an electron transport layer, tris (8-quinolinolato) aluminum, trinitrofluorenone, anthraquinodimethane, fluorenylidenemethane, tetracyanoethylene, fluorenone, diphenoquinone oxadiazole, anthrone, thiopyranji Oxides, diphenoquinone, benzoquinone, malononitrile, nitroanthraquinone, oxodiazole, triazole, silole, hydroxyflavone-beryllium complex, or derivatives thereof can be used. These electron transport layer materials may be mixed with the organic light emitting layer 25 or the electron injection layer 26.

In Example 10 described above, polyvinylphenol (PVP) was used as the insulating layer material for defining the light emitting pixels. In addition, polyimide, polyamide, polyester, polyacrylate, polychloropyrene, polyoxymethylene, and polyvinyl chloride were used. Polyvinylidene fluoride, cyanoethyl pullulan, polymethyl methacrylate, polyimide photo radical polymerization system, photo cation polymerization system photo-curing resin, or a copolymer containing an acrylonitrile component can also be used.
[Production of solar cells]

  In this example, a solar cell was fabricated in which the film formation region of the organic semiconductor film was defined by the self-assembled monolayer formed on the transparent electrode.

DESCRIPTION OF SYMBOLS 1 ... Substrate, 2 ... Gate insulating film, 3c ... Source electrode, 3d ... Drain electrode, 4 ... High molecular organic semiconductor film, 5 ... 1st SAM film, 5a ... area | region, 6 ... 2nd SAM film, 7 ... Metal mask, 8 8a ... solution, 10 ... syringe, 11, 11a ... solution, 12 ... gate electrode, 21 ... substrate, 22 ... ITO film, 22a ... region, 23 ... hole injection layer, 24 ... hole transport layer, 25 ... organic Light emitting layer, 26 ... electron injection layer, 27 ... cathode layer, 28 ... first SAM film, 29 ... second SAM film, 30 ... photomask

Claims (12)

A method for manufacturing a semiconductor device comprising a substrate on which an organic semiconductor film is formed in a predetermined region,
A second self-assembled monolayer having a contact angle between the first region in which the first self-assembled monolayer is formed and a predetermined solvent is smaller than that of the first self-assembled monolayer. A coating step of coating the substrate with a solution comprising the solvent and the organic semiconductor material in a state where the substrate having the second region formed is at a predetermined temperature or higher;
And a removing step of removing the solution covering the first region. A method for manufacturing a semiconductor device, comprising: The method of manufacturing a semiconductor device according to claim 1, wherein the organic semiconductor material is a polymer organic semiconductor material. The method of manufacturing a semiconductor device according to claim 1, wherein the covering step is a step of immersing the substrate in the solution. In the coating step, the substrate is coated with the solution using one or more methods selected from the group consisting of dip coating, drop casting, spray coating, screen printing, gravure printing, flexographic printing, and inkjet printing. The method of manufacturing a semiconductor device according to claim 1, wherein the method is a process. 5. The method of manufacturing a semiconductor device according to claim 1, wherein in the covering step, the temperature of the solution is equal to or higher than the predetermined temperature. 6. 6. The method of manufacturing a semiconductor device according to claim 1, wherein in the covering step, the temperature of the substrate is a temperature of 30 ° C. or more and a boiling point or less of the solvent. The method of manufacturing a semiconductor device according to claim 1, wherein the removing step is a step of tilting at least the first region of the substrate with respect to a horizontal plane. . The method for manufacturing a semiconductor device according to claim 7, wherein, in the removing step, an inclination angle of the first region with respect to a horizontal plane is 20 ° or more. In the removing step, the inclination angle of the first region with respect to the horizontal plane is 30 ° or more,
The predetermined temperature is 40 ° C. or higher and a temperature not higher than the boiling point of the solvent;
The method of manufacturing a semiconductor device according to claim 7, wherein X + Y ≧ 120 is satisfied when the predetermined temperature is X ° C. and the inclination angle is Y °. The semiconductor device is a thin film transistor,
The method for manufacturing a semiconductor device according to claim 1, wherein the organic semiconductor film is a channel portion in the thin film transistor. The semiconductor device is an organic electroluminescence element,
The method for manufacturing a semiconductor device according to claim 1, wherein the organic semiconductor film is a layer in contact with a transparent electrode in the organic electroluminescence element. The semiconductor device is a solar cell,
The said organic-semiconductor film is a layer which contact | connects the transparent electrode in the said solar cell. The manufacturing method of the semiconductor device of any one of Claims 1-9 characterized by the above-mentioned.