JP2008053582A - Method of manufacturing electronic device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To solve the problem that while it is needed to detect a pattern position and align the pattern with a printing position in order to form an electronic device by a contact print method, the alignment is particularly difficult because, when a self-assembled monolayer (SAMs) is used for a liquid-repellent film, a level difference is the equivalent of one molecule, which is difficult to be optically identified, and there remains a region in which a component precursor is not filled enough even if a self alignment mechanism exists. <P>SOLUTION: An inkjet method is used to drop a silver-dispersed liquid in an alignment mark region 24 that is surrounded by the liquid-repellent film. Since the inside of the alignment mark region 24 is highly lyophilic, the silver-dispersed liquid spreads. In a region outside the alignment mark region, the silver-dispersed liquid is rejected by the liquid-repellent self-assembled monolayer 22, and pulled into a realignment mark region by surface tension, thus making it possible to form an alignment mark structure 31. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an electronic device manufacturing method.

  The following techniques are known as methods for manufacturing electronic devices such as organic transistors, organic wirings, and piezoelectric elements. In this technique, first, a pattern using a liquid repellent film is formed on the main surface side of the substrate using a liquid repellent film forming material so as to surround the periphery of the electronic device. Next, by using a contact printing method which is one of the relief printing methods in the pattern, a liquid repellent film is avoided by using a component precursor obtained by liquefying a substance used as a component of an electronic device. It is a technique for forming a component of an electronic device by forming it on a pattern and then solidifying it.

  By using this technique, it is possible to correct a printing misalignment that inevitably occurs in the printing method, represented by the contact printing method, by self-alignment. Specifically, when a positional deviation of, for example, about 1 μm occurs in the printing method, a part of the component precursor is formed so as to get over a region having high liquid repellency surrounding the pattern. In the region having high liquid repellency, the component precursor is repelled. Further, since the surface tension works, it is pulled back so as to be sucked into the pattern having low liquid repellency. Therefore, the remaining amount of the component precursor in the region overcoming the pattern is suppressed.

  On the other hand, since the lyophilicity of the unfilled area in the pattern caused by the printing misalignment is higher than that of the surrounding area, the constituent element precursor in the pattern diffuses to spread. Therefore, a component precursor is also formed in the unfilled region. With these mechanisms, printing misalignment is corrected by self-alignment. Patent Document 1 describes an example in which this technique is used for forming a piezoelectric pattern.

JP 2005-72473 A

  However, in order to form an electronic device by the contact printing method, it is necessary to detect the position of the pattern and to align the pattern and the printing position. In particular, when self-assembled monomolecular films (SAMs) are used for the liquid repellent film, the level difference generated in the liquid repellent film is one molecule, and optical recognition is almost impossible. Therefore, it is extremely difficult to perform alignment for aligning the pattern and the printing position. When the printing misalignment is large, the component precursor is left in a region having high liquid repellency even when the self-alignment mechanism by the above-described mechanism is present, and there is a diffusion mechanism due to bleeding that occurs in an unfilled region in the pattern. Even in this case, there is a problem that a region where the filling with the component precursor is insufficient remains.

  Accordingly, an object of the present invention is to provide a method for manufacturing an electronic device that can solve the conventional problems and can detect the position of a pattern even when a self-assembled monolayer is used.

In the present application, “upper” is defined as a direction away from the main surface of the substrate.
In order to solve the above-described problems, the method of manufacturing an electronic device according to the present invention includes: (1) a functional film configuration on the main surface side of a substrate, of the substances constituting the electronic device, located closest to the main surface side; A second liquid containing a liquid precursor of the substance and an alignment mark region and the liquid precursor for a first liquid containing an alignment mark structure precursor for obtaining an alignment structure having different optical properties from the surroundings. Forming a lyophilic film having a higher lyophilic property than the lyophilic state on the main surface side so as to include at least a region to be positioned, and (2) compared with the lyophilic state on the main surface side Forming a liquid repellent film having low lyophilicity with respect to the first liquid and the second liquid so as to surround the alignment mark region and the region where the liquid precursor is to be located; and (3) the alignment The first in the mark area A step of applying energy to the first liquid after applying the liquid to form the alignment mark structure; and (4) performing alignment using the alignment mark structure, and then patterning the second liquid. The alignment mark region has a pattern that includes a displacement of the attachment position of the second liquid caused by an alignment error that occurs when the second liquid is applied, and ) And step (2) are executed in this order, steps (2) and (1) are executed in this order, only step (2) is executed, or only step (1) is executed, After performing any one of these four methods, the steps (3) and (4) are performed in this order.
Here, the “functional film” is defined as including a semiconductor film functioning as a channel region of a transistor and a metal film functioning as a gate electrode or a wiring.

  According to this manufacturing method, the alignment mark region is set so as to include a deviation in the adhesion position of the liquid containing the alignment mark structure precursor. For this reason, self-alignment is performed by applying liquid to a position where the alignment mark structure precursor can be drawn into the lyophilic film inside the alignment mark area, based on the shape around the substrate. Thus, an alignment mark structure can be formed. Therefore, it is possible to provide a method for forming an alignment mark structure that does not depend on the position where the liquid is attached, and it is possible to ensure higher positional accuracy than when the alignment mark structure is not formed by self-alignment.

  In addition, in the method for manufacturing an electronic device according to the present invention, the main surface of the substrate is compared with the first liquid containing the alignment mark structure precursor and the second liquid containing the functional film precursor on the main surface side of the substrate. A lyophilic film having a higher lyophilic property than the lyophilic state on the side, and a lower lyophilic property relative to the lyophilic state on the main surface side of the substrate relative to the first liquid and the second liquid Forming a first region where a liquid repellent film having a property overlaps, and a second region where only the lyophilic film is disposed without overlapping the lyophilic film and the liquid repellent film; Applying the first liquid to the first portion to be the alignment mark in the second region, forming the alignment mark structure, and performing alignment using the alignment mark structure, The second liquid is applied to a second portion where the functional film is to be formed in the second region. It was applied, and forming the functional film, may include a.

  In the method of manufacturing an electronic device, the step of applying the second liquid to the second portion of the second region may contact a master having irregularities on the main surface side of the substrate, and the master It is preferable that the second liquid disposed in the recess is transferred to the second portion of the second region. According to this, the precision of alignment at the time of pressing a master can be improved.

  Moreover, the alignment mark structure which functions as a pattern for optical position recognition is formed by using the member from which an optical characteristic differs from the periphery as an alignment mark structure. Since the optical characteristics are different, the position of the alignment mark structure can be easily detected when light is irradiated.

  Therefore, highly accurate alignment can be easily performed by performing alignment using this alignment mark structure.

  In order to solve the above-described problem, the electronic device manufacturing method of the present invention is characterized in that the application of the first liquid is performed using a deposition process by a dispense method or an inkjet method.

  According to this manufacturing method, the liquid alignment mark structure precursor is deposited on the lyophilic film by the dispensing method or the inkjet method. Since the dispensing method and the ink jet method can precisely control the discharge amount, it is possible to supply a certain amount of the alignment mark structure precursor. Therefore, it is possible to suppress changes in the shape of the alignment mark structure due to fluctuations in the supply amount of the alignment mark structure precursor, and it is possible to perform more precise alignment.

  In order to solve the above-described problem, in the method for manufacturing an electronic device according to the present invention, the application of the first liquid is performed using a deposition process by a dispense method or an inkjet method, and at the same time as the deposition process or The alignment mark structure precursor deviated on the liquid-repellent film by applying one or both of vibration energy and thermal energy after the deposition step is pulled back to the liquid-philic film and the alignment mark in the liquid-philic film The absolute amount of film thickness unevenness of the structure precursor is suppressed.

  According to this manufacturing method, when the liquid alignment mark structure precursor corresponding to a state having a minimum value of energy is left in the liquid-repellent film, the minimum value of energy is applied by applying energy. It is possible to promote the movement to the lyophilic film, which escapes the state and has a minimum energy value, and an alignment mark structure having more precise self-alignment can be formed. Further, by suppressing the absolute amount of uneven distribution of the alignment mark structure precursor in the lyophilic film, irregular reflection is suppressed and alignment accuracy can be improved.

  In order to solve the above-described problems, in the method of manufacturing an electronic device according to the present invention, the lyophilic film and the lyophobic film are optically transparent, and the alignment mark structure precursor includes Ag, Au. , Using a material imparted with fluidity by including metal fine particles containing at least one of Cu in a solvent, the alignment mark structure includes a metal derived from the alignment mark structure precursor, and the substrate One or more alignment mark structures are provided on the main surface side.

  According to this manufacturing method, Ag, Au, and Cu having high light reflectivity are used as the alignment mark structure, so that the light reflectivity differs greatly between the region where the alignment mark structure is formed and other regions. Therefore, the alignment mark structure can be easily recognized as compared with the case where a material having low light reflectance is used for the alignment mark structure. In addition, when a single alignment mark structure is used, the area required for alignment can be reduced, and when a substrate having the same area is used, the chip on which the electronic device is formed can be obtained from one substrate. You can increase the number. In addition, when a plurality of alignment mark structures are used, precise alignment that can be corrected against deformation of the substrate can be performed.

  In order to solve the above-described problems, the electronic device manufacturing method of the present invention is characterized in that at least one of the lyophilic film and the liquid-repellent film is formed of a self-assembled monomolecular film.

  According to this manufacturing method, when a self-assembled monomolecular film is used as the liquid repellent film, the level difference caused by the formation of the liquid repellent film becomes the thickness of one molecule, and the level difference can be extremely small. Therefore, it is possible to form an electronic device with excellent flatness that eliminates distortion caused by a step.

  In addition, when a self-assembled monomolecular film is used for the lyophilic film, in addition to eliminating distortion caused by a step, the lyophilic film can be provided with high orientation that occurs due to self-assembly. By forming a film over this lyophilic film, the orientation of the film can be improved, and the characteristics of the electronic device sensitive to the orientation of the film can be controlled.

  When both use self-assembled monolayers, the liquid repelled from the lyophobic film flows into the lyophilic film, and the liquid is redistributed so as to ooze inside the lyophilic film, and the inside of the lyophilic film is Since all the liquid is filled and no liquid remains on the liquid repellent film, a manufacturing method having higher self-alignment property can be provided.

  In order to solve the above-described problems, a method of manufacturing an electronic device according to the present invention includes a fluorinated alkylsilane having liquid repellency as a constituent element of the self-assembled monolayer and an aminoalkyl having lyophilicity. It contains at least one of silane.

  According to this production method, self-organized monomolecules having higher self-alignment properties by using fluorinated alkylsilane as a material having excellent liquid repellency and aminoalkylsilane having excellent lyophilic properties A method for manufacturing a membrane can be provided.

  In order to solve the above-described problem, the electronic device manufacturing method according to the present invention includes a bottom gate type organic thin film transistor (TFT), and the alignment mark structure is used to position the electronic device. Next, the gate electrode precursor of the organic thin film transistor is formed using a contact printing method of any one of a contact printing method, a relief printing method, an intaglio printing method, a screen printing method, and a flat plate printing method. It is characterized by.

  According to this manufacturing method, alignment is performed using the alignment mark structure, and the gate electrode precursor is formed on the main surface side of the substrate with the amount of misalignment being suppressed. Here, the gate electrode precursor formed around the region surrounded by the liquid-repellent film is repelled from the position of the gate electrode region of the organic thin film transistor. Further, since the surface tension works, the gate electrode precursor is pulled back to the gate electrode region so that it is absorbed into the pattern having low liquid repellency. Therefore, it is possible to form the gate electrode in a state of alignment by self-alignment. Therefore, it is possible to provide a method for manufacturing a bottom gate type organic thin film transistor as an electronic device in which the occurrence of defects due to misalignment is suppressed. The misalignment amount is desirably aligned so that an isolated gate electrode precursor is not generated on the liquid repellent film, and the misalignment amount is preferable by performing alignment with the alignment mark structure. It becomes possible to limit to the range.

  In addition, in order to solve the above-described problems, the electronic device manufacturing method according to the present invention is such that the electronic device is a top-gate organic thin film transistor, and the position of the channel region of the organic thin film transistor is determined using the alignment mark structure. A contact printing method of any one of a contact printing method, a relief printing method, an intaglio printing method, a screen printing method, and a lithographic printing method is performed on the channel region formed so as to be surrounded by the liquid repellent film. The channel structure precursor of the organic thin film transistor is formed by using the method.

  According to this manufacturing method, alignment is performed using the alignment mark structure, and the channel structure precursor is formed on the main surface side of the substrate in a state where the amount of misalignment is suppressed. Here, the channel structure precursor formed outside the position of the channel region of the organic thin film transistor and formed around the region surrounded by the liquid repellent film is repelled. Furthermore, since the surface tension works, the channel structure precursor is pulled back to the channel region so that it is absorbed into the pattern having low liquid repellency. Therefore, the channel structure can be formed in a state where alignment is performed by self-alignment. Therefore, it is possible to provide a method for manufacturing an organic thin film transistor as an electronic device that suppresses the occurrence of defects due to misalignment. The misalignment amount is preferably aligned so that no isolated channel structure precursor is generated on the liquid repellent film, and the misalignment amount can be reduced by performing alignment with the alignment mark structure. It becomes possible to suppress to a preferable range.

  In order to solve the above-described problem, in the method for manufacturing an electronic device according to the present invention, the channel structure is formed on a part of the lyophilic film, and the lyophilic film is a self-assembled monolayer. The channel structure is provided with orientation by the self-assembled monolayer.

  According to this manufacturing method, it is possible to improve the performance of the organic thin film transistor whose electric characteristics strongly depend on the degree of orientation of the channel structure. The orientation obtained by the lyophilic self-assembled monolayer is transferred to the channel structure portion of the organic transistor. Therefore, the electrical characteristics of the channel portion of the organic thin film transistor can be improved.

  Self-assembled monolayers (SAMs) are methods for fixing molecules to a solid surface and capable of forming highly oriented and dense molecular films (SA: Self-Assembled Monolayers). It is a film produced by the Assembly method. The self-assembly method can manipulate the molecular orientation on the order of angstroms.

  For this reason, it is possible to form a thin film whose properties are affected by the orientation on the self-assembled monomolecular film with a high orientation, and for an electronic device that depends on the orientation. Characteristics can be improved. Accordingly, it is possible to improve the performance of the organic transistor whose electric characteristics strongly depend on the degree of orientation of the channel region. A highly oriented structure that can be obtained using a self-assembled monolayer is transferred to the channel portion of the organic transistor. Therefore, the electrical characteristics of the channel portion of the organic transistor can be improved.

  In order to solve the above-described problem, the electronic device manufacturing method of the present invention is a piezoelectric element using a ferroelectric material, and the alignment mark structure is used to align the electrode region. Then, the ferroelectric electrode precursor is formed using a contact printing method of any one of a relief printing method, an intaglio printing method, a screen printing method, and a flat plate printing method.

  According to this manufacturing method, alignment is performed using the alignment mark structure, and the electrode precursor is formed on the main surface side of the substrate in a state where the amount of misalignment is suppressed. Here, the electrode precursor that is out of the position of the electrode region of the piezoelectric element and is formed around the region surrounded by the liquid repellent film is repelled. Furthermore, since the surface tension works, the electrode precursor is pulled back to the electrode region so as to be sucked into the pattern having low liquid repellency. Therefore, it is possible to form the electrode in a state of alignment by self-alignment. Therefore, it is possible to provide a method for manufacturing a piezoelectric element as an electronic device that suppresses the occurrence of defects due to misalignment.

  Also, in the method for manufacturing an electronic device according to the present invention, the first droplet including the alignment mark structure precursor and the second droplet including the functional film precursor are formed on the main surface side of the substrate. A step of forming a lyophilic region having a higher lyophilic property than the lyophilic state on the main surface side, applying the first droplet to the first portion of the lyophilic region, and the alignment mark structure Forming an object, performing alignment using the alignment mark structure, bringing a master having irregularities into contact with a main surface side of the substrate, and bringing the second droplet disposed in the recess of the master into the And transferring to the second part of the second region to form the functional film.

  In the electronic device manufacturing method, the lyophilic region is formed on the main surface of the substrate, and the lyophilic solution on the main surface side of the substrate with respect to the first liquid and the second liquid. A region surrounded by a self-assembled monolayer having higher lyophilicity than the state is preferable.

(First embodiment)
Hereinafter, the present embodiment will be described with reference to the drawings. 1 to 8 are schematic cross-sectional views showing steps of forming a bottom gate type organic thin film transistor.
First, as shown in FIG. 1 as step 1, a parylene resin film 12 is formed as a buffer film on a substrate 11 formed using polycarbonate. Here, polycarbonate is used as the substrate 11, but in the case of plastic, a material such as polyethylene terephthalate, polyethylene naphthalate, polyether sulfone, polyarylate, polycycloolefin, polyimide, or the like may be used. The material of the substrate 11 is not limited to plastic, and materials such as silicon, glass, stainless steel, and ceramic may be used. Further, the formation of the parylene resin film 12 serving as a buffer film can be omitted depending on the type of the substrate 11 and the required characteristics.

  Next, as shown in FIG. 2 as step 2, a pattern is formed using contact printing so that the periphery of the gate electrode region 23 and the alignment mark region 24 is surrounded by the liquid repellent self-assembled monolayer 22. As a precursor for forming the liquid repellent self-assembled monolayer 22, for example, fluorinated alkylsilane can be used. Alternatively, after forming the lyophobic self-assembled monolayer 22, a lyophilic self-assembled monolayer 25 having lyophilic properties may be formed inside the gate electrode region 23 and / or the alignment mark region 24. good. As a precursor for forming the lyophilic self-assembled monolayer 25, for example, aminoalkylsilane can be used. Here, the step of forming the liquid-repellent self-assembled monolayer 22 and the order of forming the lyophilic self-assembled monolayer 25 may be reversed. Alternatively, only the lyophilic self-assembled monolayer 25 may be formed.

  Here, a contact printing method that is preferably used when forming the liquid repellent self-assembled monolayer 22 will be briefly described. The contact printing method, which is one of the letterpress printing methods, is one of the nanostructure forming methods, and the pattern is transferred by pressing the stamp 21 (master disc). The stamp 21 is produced by copying a fine shape pattern (master) produced by known optical lithography or electron beam lithography onto rubber-like plastics. In the contact printing method, a liquid substance is applied to the printing surface side of this stamp and brought into close contact (contact) with the substrate, and the pattern of the convex portion of the stamp that is in close contact with the substrate is transferred to the same pattern as the master on the substrate. It is a method to do. As a manufacturing method of the master substrate, a method of forming a master substrate by using a photolithographic method, or an electron beam exposure capable of further fine processing in place of light in an exposure process used in the photolithographic method is used. The means for forming can be used. By forming the liquid-repellent self-assembled monolayer 22 using this stamp 21, a fine pattern on the order of μm can be easily formed at a low cost. Further, by using the contact printing method, it is possible to form a fine pattern with higher film thickness accuracy than the dispensing method or the ink jet method.

  The stamp 21 used in the contact printing method is formed with a precursor of the liquid repellent self-assembled monolayer 22 for forming the liquid repellent self-assembled monolayer 22. As a precursor of the liquid repellent self-assembled monolayer 22, for example, fluorinated alkylsilane can be used. Then, the liquid repellent self-assembled monolayer 22 formed on the convex portion of the stamp 21 is transferred onto the parylene resin film 12 to form the liquid repellent self-assembled monolayer 22. The transfer is performed by bringing the convex portion of the stamp 21 into contact with the parylene resin film 12. Since the stamp 21 suffers little damage in this transfer process, it can be used again, and TAT and cost can be reduced.

  Next, as step 3, as shown in FIG. 3, an alignment mark structure precursor 32 formed by dispersing silver fine particles in ethanol in the alignment mark region 24 is filled. Specifically, the alignment mark region 24 is filled with the alignment mark structure precursor 32 by using a dispensing method in which a liquid material is locally dropped or an inkjet method (liquid silver is ejected instead of ink).

  The dispensing method and the ink jet method are suitable for supplying a large amount of liquid material, and by supplying the liquid material so as to fill the alignment mark region 24, the spread is suppressed by the surface tension, that is, the alignment mark. An alignment mark structure 31 is formed so as to cover the region 24. Since the liquid supply by the dispensing method or the ink jet method is performed with high controllability, the alignment mark structure 31 can be formed with high shape reproducibility. Here, the alignment mark region 24 is formed with a large dimension, for example, about 100 μm on a side. Therefore, liquid silver can be filled into the alignment mark region 24 based on information such as a relative positional relationship with the substrate 11 formed using polycarbonate.

  After filling, the alignment mark region 24 is filled with silver as the alignment mark structure 31 by volatilizing and removing ethanol. Since silver has a very high reflectance, the contrast difference between the alignment mark structure 31 formed by filling with silver and the surrounding area becomes large, and the alignment mark structure 31 that can be easily aligned is formed. Here, the alignment mark structure precursor 32 filling the alignment mark region 24 is formed by dispersing gold or copper fine particles in ethanol instead of liquid silver in which silver fine particles are dispersed in ethanol. A liquid material or a mixture thereof may be used. In addition, ethanol was used as the dispersion medium here, but this may be, for example, an alcohol such as propanol or butanol, or a solvent such as ether or ketone. It is preferred to use no solvent. A plurality of alignment mark regions 24 are preferably formed on the substrate 11, and alignment can be performed with higher accuracy by performing alignment with reference to the alignment mark structures 31 formed at a plurality of positions. .

  Next, as step 4, as shown in FIG. 4, alignment is performed in accordance with the position of the alignment mark structure 31 having a higher reflectance than the periphery, and the gate electrode precursor 41 is filled on the gate electrode region 23. Since the liquid repellent self-assembled monolayer 22 is formed so as to surround the gate electrode region 23, the gate electrode precursor 41 can be filled by self-alignment if approximate positioning can be performed.

  When a plurality of alignment mark structures 31 are provided, the positioning accuracy is high, and therefore it is preferable that the gate electrode precursor 41 can be filled more reliably. Here, as a constituent material of the gate electrode precursor 41, a metal typified by gold, silver, or copper is made fine particles and dispersed in a solvent, or polyaniline, polyethylenedioxythiophene / polystyrene sulfonic acid (PEDOT / PSS). ) Or the like in which a conductive polymer is dissolved in a solvent to give fluidity. In order to form the gate electrode precursor 41 using the conductive polymer, for example, when polyaniline is used, a material dissolved using an organic solvent such as butanol can be used as the gate electrode precursor 41. In the present embodiment, a liquid in which silver fine particles are dispersed in ethanol is used.

  The liquid gate electrode precursor 41 is formed using, for example, the same contact printing method as the method of forming the liquid repellent self-assembled monolayer 22. As described above, the contact printing method is a technique suitable for forming a fine pattern. Here, since the gate electrode precursor 41 is surrounded by the liquid-repellent self-assembled monolayer 22, the gate electrode precursor 41 riding on the liquid-repellent self-assembled monolayer 22 is caused by the surface tension. Since it is pulled back to the region 23, the gate electrode precursor 41 can be formed by self-alignment.

  After the gate electrode region 23 is filled with the gate electrode precursor 41, the solvent is removed by volatilization to solidify the gate electrode 42. With this process, the volume shrinks as shown in FIG. Here, a method using a contact printing method is illustrated as a method for forming the gate electrode precursor 41. This is representative of a relief printing method, an intaglio printing method, a screen printing method, and a flat printing method instead of the contact printing method. Can be used. The contact printing method is suitable for forming a fine pattern because a precise pattern can be handled.

  Further, since the gate electrode 42 is surrounded by the liquid repellent self-assembled monolayer 22, the width of the stamp 21 used in the contact printing method is reduced while the width of the liquid repellent self-assembled monolayer 22 is narrowed. By narrowing the gate electrode 42, it is possible to form a gate electrode 42 that can cope with a further fine structure.

  The gate electrode 42 is formed on the parylene resin film 12. Since the parylene resin film 12 is more lyophilic than the liquid repellent self-assembled monolayer 22 surrounding the gate electrode 42, it can ensure good adhesion and suppress the occurrence of defects such as film peeling. be able to.

  Next, as step 5, a gate insulating film 51 is formed as shown in FIG. The gate insulating film 51 is formed by forming a gate insulating film precursor using a contact printing method typified by a contact printing method and solidifying it. As a material constituting the gate insulating film 51, an organic film such as parylene, polyacrylonitrile, polyvinylphenol, epoxy resin, epoxy / silicone hybrid, or an inorganic film such as silicon oxide can be used. As an example, when parylene resin is used for the gate insulating film 51, a liquid in which parylene resin is dissolved in butanol can be used as a gate insulating film precursor. The gate insulating film 51 is typically formed to have a thickness of about 200 nm.

  Next, as step 6, source / drain electrodes 61 are formed as shown in FIG. The source / drain electrode 61 is formed by depositing and solidifying the source / drain electrode precursor 62 using a contact printing method typified by a contact printing method. Constituent materials are the same as the constituent materials of the gate electrode, but metal such as gold, silver and copper are finely powdered and dispersed in a solvent, polyaniline, polyethylenedioxythiophene / polystyrene sulfonic acid (PEDOT / PSS) A material obtained by imparting fluidity to a conductive polymer such as the above can be used. In the present embodiment, silver is used for the source / drain electrode 61, and in the present embodiment, a liquid material in which silver fine particles are dispersed in ethanol is used as the source / drain electrode precursor 62.

  Next, as step 7, as shown in FIG. 7, a semiconductor film 71 is formed. The semiconductor film 71 is formed using a contact printing method. As a constituent material of the semiconductor film 71, polythiophene, polyfluorene, pentacene, or the like can be used. As an example, when polythiophene is used for the semiconductor film 71, a liquid obtained by dissolving polythiophene in butanol can be used as the semiconductor film precursor 72 as a liquid material that can be handled by the contact printing method. The semiconductor film precursor 72 is formed by contact printing so that the semiconductor film 71 has a thickness of about 100 nm. After the contact printing method is used, the organic thin film transistor 73 is formed by evaporating and removing the solvent to solidify.

  Next, as step 8, as shown in FIG. 8, an ITO electrode 81 and a protective layer 82 are formed to form a liquid crystal driving element 83. The thickness of the ITO electrode 81 is, for example, about 150 nm, and the protective layer 82 is made of parylene resin so as to have a thickness of about 1 μm. Since parylene resin has extremely low water vapor and gas permeability, the organic thin film transistor 73 and the ITO electrode 81 can be effectively protected. In addition, this embodiment can be easily diverted as a manufacturing process of an inorganic thin-film transistor by using silicon or a compound semiconductor for the semiconductor film 71.

(Second Embodiment)
Next, a second embodiment will be described with reference to the drawings. 9 to 12 are schematic cross-sectional views showing a process for forming a top gate type organic thin film transistor. Here, in order to avoid redundant description, description of parts common to the first embodiment is omitted. Further, the effects of the quoted portion from the first embodiment inherit the effects of the first embodiment unless otherwise specified.

  First, after the steps 1, 2, and 3 according to the first embodiment, as shown in FIG. 9, alignment is performed in accordance with the position of the alignment mark structure 31, and a semiconductor film pattern is formed using a contact printing method or the like. The inside of 91 is covered with a lyophilic self-assembled monolayer 92 using a material having lyophilicity and self-organizing characteristics such as aminoalkylsilane. The position surrounding the lyophilic self-assembled monolayer 92 is covered with the liquid repellent self-assembled monolayer 22. The inside of the semiconductor film pattern 91 is covered with a lyophilic self-assembled monolayer 92, and the outside is covered with a lyophobic self-assembled monolayer 22. The procedure for forming the lyophilic self-assembled monolayer 92 and the procedure for forming the lyophobic self-assembled monolayer 22 can be interchanged. Alternatively, a procedure for forming only one of the lyophilic self-assembled monolayer 92 or the lyophobic self-assembled monolayer 22 may be used.

  By this step, the orientation in the semiconductor film pattern 91 can be made uniform. In particular, when the semiconductor film 101 (see FIG. 10) is formed using an organic semiconductor, the electrical characteristics of the organic thin film transistor 114 (see FIG. 11) shown in FIG. 11 can be improved by aligning the orientation.

  Next, as shown in FIG. 10, a semiconductor film 101 is formed in a semiconductor film pattern 91 having a uniform orientation. The semiconductor film 101 is formed by using a liquid material as a precursor of the semiconductor film 101 by a contact printing method represented by a contact printing method, a relief printing method, an intaglio printing method, a screen printing method, and a flat plate printing method. And formed by curing. As a constituent material of the semiconductor film 101, polythiophene, polyfluorene, pentacene, or the like can be used. As an example, when polythiophene is used for the semiconductor film 101, a liquid obtained by dissolving polythiophene in butanol can be used as the semiconductor film precursor 102 as a liquid material that can be handled by the contact printing method. The semiconductor film precursor 102 is formed using a contact printing method so that the semiconductor film 101 has a thickness of about 100 nm.

  Next, as shown in FIG. 11, Step 4 according to the first embodiment is performed, and the source / drain electrodes 112 are formed by the contact printing method, and subsequently, Step 5 according to the first embodiment is performed to perform gate insulation. A film 111 is formed. Subsequently, by forming the gate electrode 113, for example, an organic thin film transistor 114 is formed.

  Here, as a constituent material of the precursor of the gate electrode 113, a metal typified by gold, silver, or copper is made into fine particles and dispersed in a solvent, polyaniline, polyethylenedioxythiophene / polystyrene sulfonic acid (PEDOT / A material obtained by dissolving a conductive polymer such as PSS) in a solvent and imparting fluidity can be used. In order to form a gate electrode precursor using a conductive polymer, for example, when polyaniline is used, a material dissolved using an organic solvent such as butanol can be used. In the present embodiment, a liquid in which silver fine particles are dispersed in ethanol is used.

  Next, step 8 according to the first embodiment is performed. As shown in FIG. 12, the liquid crystal driving element 123 is formed by forming the ITO electrode 121 and the protective layer 122. The thickness of the ITO electrode 121 is, for example, about 150 nm, and the protective layer 122 is made of parylene resin so as to have a thickness of about 1 μm. Since parylene resin has extremely low water vapor and gas permeability, the organic thin film transistor 114 and the ITO electrode 121 can be effectively protected.

  When this manufacturing method is used, the semiconductor film 101 is formed in a portion having a flat base shape as shown in FIG. Since the transistor characteristics are governed by the characteristics of the semiconductor film 101, the top gate type structure used in this embodiment formed in a place where the base shape is flat is suitable for improving the characteristics of the semiconductor film 101. is there. In addition, the semiconductor film 101 is formed in a region where the orientation is uniformed by forming the lyophilic self-assembled monolayer 92. Therefore, the orientation of the semiconductor film 101 is uniform, and the organic thin film transistor 114 with more excellent characteristics can be formed.

  Further, in place of the method of forming the lyophilic self-assembled monomolecular film 92 and aligning the alignment, the alignment is aligned by a process of rubbing the substrate 11 or the parylene resin film 12 formed using polycarbonate. It may be processed.

  Even in this case, by using silicon or a compound semiconductor for the semiconductor film 101, the present embodiment can be easily used as a manufacturing process of an inorganic thin film transistor.

(Third embodiment)
Next, a third embodiment will be described with reference to the drawings. 13 to 17 are schematic cross-sectional views showing a process for forming a ferroelectric film. Here, in order to avoid redundant description, description of parts common to the first embodiment is omitted. Further, the effects of the quoted portion from the first embodiment inherit the effects of the first embodiment unless otherwise specified.

  First, after step 1 according to the first embodiment is finished, as shown in FIG. 13, the periphery of the ferroelectric film electrode pattern 131 and the alignment mark region 24 is formed as a liquid-repellent self-assembled monomolecule using a contact printing method. A pattern is formed so as to be surrounded by the film 132. The conditions for forming the liquid repellent self-assembled monolayer 132 are the same as those in step 2 according to the first embodiment. Subsequently, a lyophilic self-assembled monolayer 133 is formed in a region where the ferroelectric film electrode pattern 131 and the alignment mark region 24 are to be formed. The lyophilic self-assembled monolayer 133 can be formed using, for example, aminoalkylsilane. Here, the order of the step of forming the liquid repellent self-assembled monolayer 132 and the step of forming the lyophilic self-assembled monolayer 133 can be interchanged. In addition, either the step of forming the liquid repellent self-assembled monolayer 132 or the step of forming the lyophilic self-assembled monolayer 133 can be omitted.

  Next, as shown in FIG. 14, the alignment mark region 24 is filled with liquid silver as the alignment mark structure precursor 32 and dried and solidified by the same process as the process 3 according to the first embodiment. An object 31 is formed.

  Next, the same process as the process 4 according to the first embodiment is performed, and alignment is performed using the alignment mark structure 31 formed by filling with silver as shown in FIG. A driving electrode 151 is formed. The electrode 151 is formed by evaporating and removing ethanol after forming the electrode 151 by a contact printing method using a solution in which fine particles of platinum are dispersed in ethanol.

Next, as shown in FIG. 16, a piezoelectric film 161 is formed. The specific composition of the piezoelectric film 161 is not particularly limited, but lead zirconate titanate (Pb (Zr, Ti) O ₃ : PZT), lead lanthanum titanate ((Pb, La) TiO ₃ ). ), Lead lanthanum zirconate ((Pb, La) ZrO ₃ : PLZT), lead magnesium niobate titanate (Pb (Mg, Nb) TiO ₃ : PMN-PT), lead magnesium niobate zirconate titanate (Pb ( Mg, Nb) (Zr, Ti) O ₃ : PMN-PZT), lead zinc niobate titanate (Pb (Zn, Nb) TiO ₃ : PZN-PT), scandium lead niobate titanate (Pb (Sc, Nb) _{) TiO 3: PSN-PT)} , nickel niobate titanate (Pb (Ni, Nb) TiO 3: PNN-PT), (Ba 1-x Sr x) TiO 3 (0 ≦ x ≦ 0.3 _{, Bi 4 Ti 3 O 12,} SrBi 2 Ta 2 O 9, LiNbO 3, LiTaO 3, is preferably one of KNbO _3. For example, in the case of lead magnesium niobate zirconate titanate, a composition of Pb (Mg _1/3 Nb _2/3 ) _0.1 Zr _0.504 Ti _0.396 O ₃ is suitable. The piezoelectric film 161 can be deposited on the electrode 151 by contact printing, for example, in an acetic acid-based solvent.

  Next, an electrode 171 is formed on the piezoelectric film 161 as shown in FIG. The electrode 171 is formed by volatilizing and removing ethanol using a solution in which fine particles of platinum are dispersed in ethanol.

  Here, when the electrode 171 is formed, the electrode 171 may be formed so as to fit inside the piezoelectric film 161 in a plan view. In this case, the electrode 151 and the electrode 171 can be electrically insulated with high certainty. Through this process, a piezoelectric element 172 as an electronic device is formed. Note that after this step, a protective layer may be formed using a valylene resin or the like. Since the parylene resin has extremely low water vapor and gas permeability, the piezoelectric element 172 can be effectively protected.

FIG. 6 is a schematic cross-sectional view illustrating a process of forming a bottom gate type organic thin film transistor. FIG. 6 is a schematic cross-sectional view illustrating a process of forming a bottom gate type organic thin film transistor. FIG. 6 is a schematic cross-sectional view illustrating a process of forming a bottom gate type organic thin film transistor. FIG. 6 is a schematic cross-sectional view illustrating a process of forming a bottom gate type organic thin film transistor. FIG. 6 is a schematic cross-sectional view illustrating a process of forming a bottom gate type organic thin film transistor. FIG. 6 is a schematic cross-sectional view illustrating a process of forming a bottom gate type organic thin film transistor. FIG. 6 is a schematic cross-sectional view illustrating a process of forming a bottom gate type organic thin film transistor. FIG. 6 is a schematic cross-sectional view illustrating a process of forming a bottom gate type organic thin film transistor. FIG. 6 is a schematic cross-sectional view showing a step of forming a top gate type organic thin film transistor. FIG. 6 is a schematic cross-sectional view showing a step of forming a top gate type organic thin film transistor. FIG. 6 is a schematic cross-sectional view showing a step of forming a top gate type organic thin film transistor. FIG. 6 is a schematic cross-sectional view showing a step of forming a top gate type organic thin film transistor. FIG. 5 is a schematic cross-sectional view showing a process for forming a ferroelectric film. FIG. 5 is a schematic cross-sectional view showing a process for forming a ferroelectric film. FIG. 5 is a schematic cross-sectional view showing a process for forming a ferroelectric film. FIG. 5 is a schematic cross-sectional view showing a process for forming a ferroelectric film. FIG. 5 is a schematic cross-sectional view showing a process for forming a ferroelectric film.

Explanation of symbols

DESCRIPTION OF SYMBOLS 11 ... Substrate, 12 ... Parylene resin film, 21 ... Stamp, 22 ... Liquid repellent self-assembled monolayer, 23 ... Gate electrode region, 24 ... Alignment mark region, 25 ... Lipophilic self-assembled monolayer, DESCRIPTION OF SYMBOLS 31 ... Alignment mark structure, 32 ... Alignment mark structure precursor, 41 ... Gate electrode precursor, 42 ... Gate electrode, 51 ... Gate insulating film, 52 ... Gate insulating film precursor, 61 ... Source-drain electrode, 62 ... Source / drain electrode precursor, 71 ... Semiconductor film, 72 ... Semiconductor film precursor, 73 ... Organic thin film transistor, 81 ... ITO electrode, 82 ... Protective layer, 83 ... Liquid crystal driving element, 91 ... Semiconductor film pattern, 92 ... Parent Liquid self-assembled monolayer 101, semiconductor film, 102 semiconductor film precursor, 111 gate insulating film, 112 source / drain electrode, 113 gate Electrode, 114 ... organic thin film transistor, 115 ... gate electrode precursor, 121 ... ITO electrode, 122 ... protective layer, 123 ... liquid crystal driving element, 131 ... ferroelectric film electrode pattern, 132 ... liquid repellent self-assembled monolayer DESCRIPTION OF SYMBOLS 133 ... Lipophilic self-organization monomolecular film | membrane, 151 ... Electrode, 161 ... Piezoelectric film | membrane, 171 ... Electrode, 172 ... Piezoelectric element.

Claims (14)

(1) The second liquid containing the liquid precursor of the functional film constituent material located closest to the main surface side among the materials constituting the electronic device on the main surface side of the substrate and the optical characteristics are the surroundings A lyophilic state on the main surface side so as to include at least an alignment mark region and a region where the liquid precursor is to be located with respect to a first liquid including an alignment mark structure precursor for obtaining a different alignment structure. Forming a lyophilic film having higher lyophilicity than
(2) A region where the alignment mark region and the liquid precursor are to be located in a liquid repellent film having a low lyophilicity with respect to the first liquid and the second liquid as compared with the lyophilic state on the main surface side Forming to surround
(3) After applying the first liquid to the alignment mark region, applying energy to the first liquid to form the alignment mark structure;
(4) performing alignment using the alignment mark structure to form a pattern of the second liquid,
The alignment mark region has a pattern including a shift in the attachment position of the second liquid caused by an alignment error that occurs when the second liquid is applied, and the steps (1) and (2) Are executed in this order, the steps (2) and (1) are executed in this order, only the step (2) is executed, or only the step (1) is executed. A method of manufacturing an electronic device, wherein the steps (3) and (4) are executed in this order after one step is executed. Higher lyophilicity than the lyophilic state on the main surface side of the substrate with respect to the first liquid containing the alignment mark structure precursor and the second liquid containing the functional film precursor on the main surface side of the substrate A first region in which a lyophilic film having a lyophilic property and a lyophobic film having a lower lyophilic property than the lyophilic state on the main surface side of the substrate overlap the first liquid and the second liquid And forming a second region in which only the lyophilic film is disposed without overlapping the lyophilic film and the lyophobic film;
Applying the first liquid to a first portion to be the alignment mark in the second region to form the alignment mark structure;
Performing alignment using the alignment mark structure, applying the second liquid to a second portion where the functional film is to be formed in the second region, and forming the functional film. A method for manufacturing an electronic device.   The step of applying the second liquid to the second portion of the second region brings the master having irregularities on the main surface side of the substrate into contact with the second liquid disposed in the recess of the master. The method for manufacturing an electronic device according to claim 2, wherein the first portion is transferred to the second portion of the second region.   3. The method of manufacturing an electronic device according to claim 1, wherein the application of the first liquid is performed using a deposition process by a dispense method or an inkjet method.   The application of the first liquid is performed using a deposition process by a dispense method or an ink jet method, and either one or both of vibration energy and thermal energy is applied at the same time as the deposition process or after the deposition process. The alignment mark structure precursor deviating on the film is pulled back to the lyophilic film, and an absolute amount of film thickness unevenness of the alignment mark structure precursor in the lyophilic film is suppressed. The manufacturing method of the electronic device in any one of 1-3.   The lyophilic film and the liquid repellent film are optically transparent, and the alignment mark structure precursor is provided with fluidity by including metal fine particles containing at least one of Ag, Au, and Cu in a solvent. A substance is used, and the alignment mark structure includes a metal derived from the alignment mark structure precursor, and has one or more alignment mark structures on the main surface side of the substrate. Item 5. A method for manufacturing an electronic device according to any one of Items 1 to 4.   6. The method of manufacturing an electronic device according to claim 1, wherein at least one of the lyophilic film and the liquid repellent film is a self-assembled monomolecular film.   The electronic device manufacturing method according to claim 7, comprising at least one of fluorinated alkylsilane having liquid repellency and aminoalkylsilane having lyophilicity as a constituent element of the self-assembled monolayer. Method.   The electronic device is a bottom gate type organic thin film transistor, and is aligned with the gate electrode region using the alignment mark structure, and subsequently, contact printing, letterpress printing, intaglio printing, screen printing, flat plate 9. The method of manufacturing an electronic device according to claim 1, wherein the gate electrode precursor of the organic thin film transistor is formed using any one of the printing methods.   The electronic device is a top gate type organic thin film transistor, aligns the channel region of the organic thin film transistor using the alignment mark structure, and then continues to the channel region formed so as to be surrounded by the liquid repellent film. The organic thin film transistor channel structure precursor is formed using a contact printing method of any one of a contact printing method, a relief printing method, an intaglio printing method, a screen printing method, and a flat printing method. Item 9. A method for manufacturing an electronic device according to any one of Items 1 to 8.   The channel structure is formed on a part of the lyophilic film, and the lyophilic film is formed of a self-assembled monolayer, and the channel structure is provided with orientation by the self-assembled monolayer. The method of manufacturing an electronic device according to claim 10.   The electronic device is a piezoelectric element using a ferroelectric material, and aligns the electrode region using the alignment mark structure, and subsequently any of a relief printing method, an intaglio printing method, a screen printing method, and a flat printing method. 9. The method of manufacturing an electronic device according to claim 1, wherein the ferroelectric electrode precursor is formed by using one contact printing method. Compared with the lyophilic state on the main surface side of the substrate, the first liquid droplet containing the alignment mark structure precursor and the second droplet containing the functional film precursor are higher on the main surface side of the substrate. Forming a lyophilic region having liquidity;
Applying the first droplet to a first portion of the lyophilic region to form the alignment mark structure;
Alignment is performed using the alignment mark structure, a master having irregularities is brought into contact with the main surface side of the substrate, and the second droplet disposed in the recess of the master is second in the second region. And a step of forming the functional film by transferring to the portion of the electronic device. The lyophilic region has higher lyophilicity than the lyophilic state on the main surface side of the substrate with respect to the first liquid and the second liquid formed on the main surface of the substrate. 14. The method for manufacturing an electronic device according to claim 13, wherein the method is a region surrounded by a self-assembled monolayer.

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