JP2008198822A - Pattern formation method, electronic device manufacturing method, and electronic device manufacturing apparatus - Google Patents

Abstract

An object of the present invention is to provide a low-cost surface treatment method to reduce the cost required for trial production of an electronic device.
A vacuum processing chamber 402 having an energy beam irradiation means 412, a gas exhaust means, and a substrate holding means 418 capable of holding a substrate 10 therein, a gas supply means, a gas exhaust means, and a substrate 10. A liquid material supply chamber 404 including a liquid material supply means 422 for supplying the liquid material onto the substrate 10 held by the substrate holding means 418, and a vacuum processing chamber 402. A transfer path that communicates with the liquid material supply chamber 404; a gate valve that opens and closes the path; a transfer means 436 that can transfer the substrate 10 between the vacuum processing chamber 402 and the liquid material supply chamber 404; An apparatus for manufacturing an electronic device comprising: a substrate carry-in port 438 communicating with at least one of a vacuum processing chamber and the liquid material processing chamber.
[Selection] Figure 11

Description

  The present invention relates to a pattern forming method, an electronic device manufacturing method, and an electronic device manufacturing apparatus.

As a method for forming a pattern of a thin film made of a functional material such as a conductive material in a process for forming an electronic device such as a semiconductor element, a method of dropping a liquid material has been proposed. In this method, a liquid material composed of a functional material and a solvent is dropped onto a substrate surface made of glass or the like, and the solvent is dried and removed to form a thin film pattern. Compared to a photolithography method conventionally used for forming a thin film pattern, there is an advantage that a large-scale facility is not required and the amount of material used can be reduced.
However, since the dropped liquid material is in an unstable state until the solvent is removed, there may arise a problem that the dropped liquid material spreads greatly on the substrate surface. Further, there may be a problem that the shape immediately after dropping remains in the outline of the film pattern as it is. As a means for suppressing such a problem, there is a method of performing liquid repellency treatment on a region other than the region where the pattern on the substrate surface is to be formed and suppressing the dropped liquid material from spreading outside the region where the pattern is to be formed. .
As such a liquid repellent treatment, a method using a compound having a high surface free energy such as a silane coupling agent treatment is known (see, for example, Patent Documents 1 and 2). Since surface treatment with a silane coupling agent can form a stable liquid-repellent region, there is an advantage that the subsequent dropping step can be performed in a free atmosphere.

Japanese Patent Laid-Open No. 2004-200244 JP 2005-109184 A

However, the surface treatment with a silane coupling agent has been a factor in increasing the cost of an electronic device using the method because the agent itself is relatively expensive. In addition, since processing takes a relatively long time, there is a problem that it is difficult to apply to trial manufacture of an electronic device.
The present invention solves this problem, and an object of the present invention is to provide a low-cost surface treatment method and reduce the cost required for trial manufacture of an electronic device.

  In order to solve the above-described problems, an electronic device manufacturing apparatus according to the present invention includes an energy beam irradiation unit, a first gas exhaust unit, and a first substrate holding unit capable of holding a substrate, in a vacuum process. A chamber, a first gas supply means, a second gas exhaust means, and a second substrate holding means capable of holding the substrate, and a liquid material is placed on the substrate held by the second substrate holding means. A liquid material supply chamber provided with a liquid material supply means for supplying; a transfer path that communicates between the vacuum processing chamber and the liquid material supply chamber; a first gate valve that opens and closes the transfer path; and the vacuum process chamber And a transporting means capable of transporting the substrate between the liquid material supply chamber and a substrate carry-in port communicating with at least one of the vacuum processing chamber and the liquid material supply chamber. .

  According to such a configuration, the region on which the pattern on the substrate is to be formed is selectively irradiated by the energy beam irradiation unit to form the dangling bond, and the region can be made lyophilic. And a thin film can be formed only in the said area | region by conveying the said board | substrate to a liquid material supply chamber, without exposing to the air | atmosphere, dripping a liquid material to the said area | region, and removing a solvent. Therefore, the substrate surface treatment can be simplified by such a configuration, and a thin film pattern can be formed at low cost by dropping the liquid material.

Preferably, the energy beam is a first electron beam.
Since the electron beam has high convergence, the region where the pattern is to be formed can be selected with high accuracy, and a high-definition thin film pattern can be formed.

Preferably, the vacuum processing chamber includes a gas supply source.
According to such a configuration, after forming a dangling bond by irradiating an area other than the area where the pattern is to be formed with an energy beam, a gas is further reacted to the area to modify the surface properties of the area. it can. As a result, by forming a more stable surface compared to the surface on which dangling bonds are formed, the influence of the gas in the liquid material supply chamber can be suppressed, and high-definition thin film patterns can be formed with high reproducibility. Can be done.

Preferably, the energy beam is a focused ion beam.
With this configuration, the thin film can be patterned even in the vacuum processing chamber. Further, it is possible to form a thin film on the surface of the substrate by irradiating the focused ion beam while supplying the assist gas from the gas supply source. Therefore, the range of processes that can be performed in the manufacturing apparatus can be expanded.

Preferably, the electronic device manufacturing apparatus includes at least the laser beam irradiation unit, a third gas exhaust unit, and a third substrate holding unit capable of holding the substrate, and the second gate valve is interposed therebetween. A laser annealing chamber communicating with the conveyance path is further provided.
With this configuration, the thin film formed in the liquid material supply chamber can be annealed in the same apparatus. Therefore, the range of processes that can be performed in the manufacturing apparatus can be further expanded.

Preferably, the electronic device manufacturing apparatus includes at least a heating unit, a second gas supply unit, a fourth gas exhaust unit, and a fourth substrate holding unit capable of holding the substrate, A heating chamber communicating with the third gate valve is further provided.
With this configuration, the thin film formed in the liquid material supply chamber can be subjected to an oxidation treatment by heating in the same apparatus. Therefore, the range of processes that can be performed in the manufacturing apparatus can be expanded.

Preferably, the manufacturing apparatus of the electronic device includes an electron beam irradiation unit capable of generating a second electron beam and irradiating the substrate with the second electron beam, and the irradiated second electron beam is the substrate. And an electron microscope chamber including a detection unit that detects a third electron beam that is reflected on the surface.
With such a configuration, it is possible to measure dimensions and evaluate shapes during the process of manufacturing an electronic device. Therefore, the time required for trial manufacture of the electronic device can be shortened.

Preferably, the electronic device manufacturing apparatus is electrically connected to an external measuring instrument and can contact a predetermined portion on the substrate, and fifth substrate holding means capable of holding the substrate. And a nanoprobe chamber communicating with the transfer path via a fourth gate valve.
With this configuration, it is possible to evaluate characteristics during the manufacturing process of the electronic device. Therefore, the time required for trial production and evaluation of the electronic device can be shortened.

  In order to solve the above problems, a pattern forming method according to the present invention includes an irradiation step of irradiating an energy beam to a first region on a substrate to form a dangling bond, and a functional material in the first region. And a liquid material dropping step for dropping a liquid material containing a solvent, and holding the substrate in a controlled atmosphere without exposing the substrate to the atmosphere between the irradiation step and the liquid material dropping step. It is characterized by. It is characterized by holding in an atmosphere.

  According to such a pattern method, an arbitrary region on the substrate can be made lyophilic, and the liquid material can be dropped onto the region while maintaining the property. Therefore, a high-definition pattern can be formed at low cost.

  In order to solve the above problems, a pattern forming method according to the present invention includes an irradiation step of irradiating a first region on a substrate with an energy beam to form a dangling bond, and combining with the dangling bond. A gas treatment step for increasing the lyophilicity of the first region with respect to a liquid material containing a functional material and a solvent by supplying a gas having a property of forming a lyophilic surface by the bonding; and A dropping step of dropping the liquid material in one region, and the substrate is not exposed to the atmosphere between the irradiation step and the gas treatment step and between the gas treatment step and the dropping step. It is characterized by holding in a controlled atmosphere.

  According to such a pattern method, the first region where the pattern is to be formed can be made more lyophilic than the dangling bond. And by hold | maintaining the said board | substrate in controlled atmosphere, a liquid material can be dripped on the said board | substrate, suppressing that the said property deteriorates. Therefore, a high-definition pattern can be formed at low cost and high reproducibility.

  In order to solve the above problems, a pattern forming method according to the present invention is an irradiation that forms a dangling bond by irradiating a second region on the substrate, which is a region other than the first region, with an energy beam. And supplying a gas having a property of bonding to the dangling bond and forming a liquid-repellent surface by the bonding, whereby the liquid repellent of the second region with respect to the liquid material containing the functional material and the solvent A gas treatment step for enhancing the property and a dropping step for dripping the liquid material in the first region, and between the irradiation step and the gas treatment step, and between the gas treatment step and the dropping step. In the meantime, the substrate is held in a controlled atmosphere without being exposed to the atmosphere.

  According to this pattern method, the periphery of the first region where the pattern is to be formed can be made liquid repellent. By holding the substrate in a controlled atmosphere, it is possible to drop droplets on the substrate while suppressing the deterioration of the properties. Therefore, a high-definition pattern can be formed at low cost and high reproducibility.

  In order to solve the above problems, an electronic device manufacturing method according to the present invention includes an irradiation step of irradiating a first region on a substrate with an energy beam to form a dangling bond, and a function in the first region. A thin film forming step of forming a thin film containing the functional material by dropping the liquid material containing the functional material and the solvent, and between the irradiation step and the thin film forming step. Is characterized in that the substrate is held in a controlled atmosphere without being exposed to the atmosphere.

  According to this manufacturing method, an electronic device can be formed starting from a thin film pattern formed without using a mask or the like. Therefore, an electronic device including a thin film pattern as a component can be manufactured at a relatively low cost.

  In order to solve the above-described problem, an electronic device manufacturing method according to the present invention includes an irradiation step of irradiating a first region on a substrate with an energy beam to form a dangling bond, and the dangling bond. A gas treatment step for improving the lyophilicity of the first region with respect to a liquid material containing a functional material and a solvent by supplying a gas having a property of forming a lyophilic surface by the bonding. A thin film forming step of forming the thin film containing the functional material by removing the solvent after dropping the liquid material on the first region, and comprising the irradiation step and the gas treatment step. The substrate is held in a controlled atmosphere without being exposed to the atmosphere, and between the gas treatment step and the thin film formation step.

  According to this manufacturing method, the first region where the pattern is to be formed can be made more lyophilic than the dangling bond. Therefore, an electronic device including a thin film pattern as a component can be manufactured with relatively low cost and high reproducibility.

  In addition, in order to solve the above-described problem, the method for manufacturing an electronic device according to the present invention forms a dangling bond by irradiating a second region on the substrate, which is a region other than the first region, with an energy beam. A functional material and a solvent are supplied by supplying a gas that does not react with the material forming the substrate and does not react with the dangling bond and has a property of making the surface liquid-repellent. A gas treatment step for increasing the liquid repellency of the second region with respect to the liquid material, and supplying the gas having the property of forming a liquid-repellent surface by bonding with the dangling bond. A gas treatment step for increasing the liquid repellency of the second region with respect to the material, and a thin film formation for forming the thin film containing the functional material by removing the solvent after dropping the liquid material on the first region And having a process Between the irradiation step and the gas treatment step, and between the gas treatment step and the thin film formation process is characterized by holding the substrate in an atmosphere which is controlled not exposed to the atmosphere.

  According to such a manufacturing method, after making the periphery of the first region where the pattern is to be formed liquid-repellent, in order to drop droplets, a much finer thin film pattern is formed, and the thin film pattern is used as a starting point. An electronic device can be formed. Therefore, it is possible to manufacture an electronic device including a thin film pattern with higher definition as a constituent element at low cost and with high reproducibility.

Preferably, after the thin film forming step, the method further includes a refining step of irradiating the peripheral portion of the thin film with a focused ion beam to shape the peripheral portion.
According to this manufacturing method, the fine thin film pattern obtained by changing the surface properties is further shaped, so that a higher definition electronic device can be manufactured at low cost.

Preferably, the functional material is silicon, and the thin film is a silicon layer.
By using a silicon pattern obtained by such a manufacturing method as a channel layer, a thin film transistor can be formed over the substrate.

Preferably, the method further includes a step of crystallization by irradiating the silicon layer with a laser beam.
With this method, the electrical characteristics of the thin film transistor having the silicon layer as a channel layer can be improved.

Preferably, the method further includes a step of forming a silicon oxide film by applying a liquid material containing at least silicon on the substrate on which the gate electrode is formed, and solidifying and oxidizing the liquid material.
The method further includes the step of forming the gate electrode by locally laminating a conductive material on the channel layer, which is a part of the silicon layer, via the silicon oxide film using a focused ion beam. Is preferred.

  Furthermore, a part of the interlayer insulating film is locally removed using a focused ion beam, and a contact hole is formed in a region that does not overlap with the gate electrode on the channel layer, and a conductive property is formed in the contact hole. Preferably, the method further includes the step of filling the material to form the source electrode and the drain electrode.

  With these manufacturing methods, it is possible to expand the range of processes that can be performed in the same apparatus, and it is possible to prototype and evaluate electronic devices at low cost.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. In the drawings shown below, the dimensions and ratios of the components are appropriately different from the actual ones in order to make the components large enough to be recognized on the drawings.

(Pattern formation method)
1 to 3, as an embodiment embodying the pattern forming method according to the present invention, an inkjet method is used to form polycrystalline silicon as a functional material on a quartz substrate (hereinafter referred to as “substrate”). A method for forming a thin film pattern will be described. The inkjet method is a method of forming a pattern by dropping a liquid material in which a pattern forming material is dissolved or dispersed, and then removing the solvent by drying.

(First embodiment)
FIG. 1 shows a pattern forming method according to a first embodiment, in which lyophilicity is improved by forming dangling bonds on a substrate surface, and a high-definition pattern is formed on the substrate. is there.

First, as shown in FIG. 1A, an electron beam 106 as an energy beam is irradiated onto a first region 100 on which a pattern on a substrate 10 held in a vacuum atmosphere is to be formed. Instead of the electron beam, an ion beam or an electromagnetic wave beam may be irradiated. In many cases, oxygen atoms 104 of quartz (silicon oxide = SiO ₂ ) constituting the substrate 10 are covalently bonded to hydrogen atoms on the surface of the substrate 10. When the electron beam 106 is irradiated to the covalent bond, hydrogen atoms are forcibly separated by impact. As a result, electrons that do not participate in bonding are generated in the first region 100, and a bond is formed. The bond is a dangling bond 102. Even when the oxygen atoms 104 on the surface of the substrate 10 are not bonded to hydrogen electrons, a part of the electrons are blown off by the impact of the irradiation and a dangling bond can be formed.

  Next, as shown in FIG. 1B, a functional liquid material 108 obtained by dispersing a silicon compound as a functional material in a solvent in a first region is dropped from a nozzle 110 of an ink jet apparatus. As described above, since the dangling bond 102 is formed in the first region, the lyophilicity is relatively improved as compared with the surrounding region. Therefore, the liquid material is suppressed from flowing out to a region other than the first region, that is, a region around the first region 100.

The silicon compound is a compound of hydrogen and silicon represented by the general formula Si _n H _m (where n represents an integer of 5 or more and m is an integer of n, 2n-2, or 2n). Those in which n is 5 or more and 20 or less are preferable, and those in which n is 5 or 6 are more preferable.
Moreover, the solvent used for the liquid material of the present embodiment is not particularly limited as long as it dissolves a solute silicon compound and does not react with the silicon compound. Specifically, hydrocarbon solvents such as toluene and xylene, or ether solvents such as ethylene glycol diethyl ether and diethylene glycol diethyl ether are preferable.

  Next, as shown in FIG. 1C, the solvent is dried and removed from the functional liquid material 108 dropped on the substrate 10 to be solidified. The solvent can be removed by drying by heating from 100 ° C to 200 ° C. Further, by heating to 300 ° C., the silicon compound can be thermally decomposed to obtain the thin film pattern 112 made of silicon fine particles.

  Finally, as shown in FIG. 1D, the thin film pattern 112 is irradiated with a laser beam 114 to be melted and recrystallized to be converted into a polycrystalline silicon film 116. The step of irradiating the laser beam is preferably performed in an atmosphere that does not contain oxygen, such as an inert gas such as nitrogen, helium, or argon, or a gas in which a reducing gas such as hydrogen is mixed in these inert gases.

According to the pattern forming method of the present embodiment, a polycrystalline silicon film having a predetermined thickness is used to make the first region 100 in which a pattern is to be formed before lysing the liquid material on the substrate 10 lyophilic. Even when a sufficient amount of liquid material is dropped to form the liquid, it is possible to prevent the liquid material from flowing out around the first region 100. In addition, since the above-described step of selectively making a part of the region on the substrate 10 lyophilic is performed by electron beam irradiation, it can be performed without using a photomask or the like. Therefore, a high-definition pattern can be obtained while suppressing an increase in cost as compared with the aspect in which the liquid material is dropped without performing the irradiation described above.
It is also possible to obtain a polycrystalline silicon film without using a laser beam by further heating after removing the solvent by drying.

(Second Embodiment)
FIG. 2 shows a pattern forming method according to the second embodiment. This embodiment differs from the first embodiment in that a dangling bond 102 formed by electron beam irradiation is not used as it is, but a pattern with improved stability and lyophilicity is obtained by using another gas. ing. Hereinafter, each process will be described with reference to the drawings.

First, as shown in FIG. 2A, an electron beam 106 as an energy beam is irradiated to a first region 100 on which a pattern on a substrate 10 held in a vacuum atmosphere is to be formed as in the first embodiment. To do. On the surface of the first region 100, hydrogen atoms covalently bonded to oxygen atoms 104 of silicon oxide (SiO ₂ ) constituting the substrate 10 are forcibly separated by impact to form a dangling bond 102.

Next, as shown in FIG. 2B, the substrate 10 is exposed to an NH ₃ gas 120 atmosphere. Since the electron beam is irradiated in a vacuum (in a vacuum chamber), if NH ₃ gas 120 is introduced into the chamber after irradiation, the surface of the substrate 10 on which the dangling bond 102 is formed is exposed to the NH ₃ gas 120. . The NH ₃ gas 120 is combined with the dangling bond 102 to form NH groups 122. Since the NH group 122 is more stable than the dangling bond 102, a surface that is more stable and improved in lyophilicity than the lyophilic surface formed by the dangling bond 102 is formed. The mode is shown in FIGS. 4 (a) to 4 (c).

As shown in FIG. 4A, the substrate surface has oxygen atoms bonded to hydrogen atoms to form OH groups. When an electron beam is irradiated to this state, as shown in FIG. 4B, hydrogen atoms are blown off by impact, and the remaining oxygen atoms are in an electrically active radical state. When NH ₃ gas is allowed to act on such a surface, as shown in FIG. 4C, oxygen atoms and NH ₃ molecules are bonded to form NH groups. The surface on which the NH group is formed is more lyophilic with respect to the functional liquid material 108 obtained by dispersing the above-described silicon compound in the solvent than the surface on which the dangling bond is formed.

  After the dangling bond 102 is formed, a functional liquid material 108 obtained by dispersing a silicon compound as a functional material in a solvent in the first region 100 as shown in FIG. Drip from 110. As described above, since the lyophilicity of the first region 100 is improved, the functional liquid material 108 is prevented from flowing out to regions other than the first region 100.

  Next, as shown in FIG. 2D, as in the first embodiment, the solvent is dried and removed from the functional liquid material 108 dropped on the substrate 10 to form a thin film pattern 112 made of silicon fine particles. obtain.

  Finally, as shown in FIG. 2E, the thin film pattern 112 is irradiated with a laser beam 114 and melted and recrystallized to obtain a polycrystalline silicon film 116.

The pattern forming method of the present embodiment is characterized in that the liquid material is dropped after the NH ₃ gas 120 is applied to the dangling bond 102 formed by electron beam irradiation. Since other molecules are bonded to oxygen radicals, a stable lyophilic surface can be obtained even in an atmosphere with a low degree of vacuum. In general, in the step of dropping a liquid material, it is difficult to maintain a degree of vacuum as high as that of a chamber in which an electron beam is irradiated due to volatilization of a solvent or the like. However, since the first region 100 where a pattern is to be formed is kept lyophilic even in an atmosphere with a low degree of vacuum, a high-definition pattern can be formed with high reproducibility.

(Third embodiment)
FIG. 3 shows a pattern forming method according to the third embodiment. Unlike the first and second embodiments, the electron beam is irradiated not on the first region 100 where a pattern is to be formed but on the second region 101 around it. Hereinafter, each process will be described.

First, as shown in FIG. 3A, an electron beam as an energy beam is applied to a second region 101 other than the first region 100 on which a pattern is to be formed on a substrate 10 held in a vacuum atmosphere. 106 is irradiated. On the surface of the second region 101, hydrogen atoms covalently bonded to oxygen atoms 104 of silicon oxide (SiO ₂ ) constituting the substrate 10 are forcibly separated by impact to form dangling bonds 102.

Next, as shown in FIG. 3B, the substrate 10 is exposed to an atmosphere of an ethylbenzene gas 126 as a gas having a property of binding the dangling bond 102 and making the surface liquid-repellent. Since the electron beam is irradiated in a vacuum (in a vacuum chamber), ethylbenzene gas 126 is introduced into the chamber after irradiation. An ethylbenzene gas 126 is bonded to the dangling bond 102 to form a CF ₃ group 128. As a result, the surface of the second region 101 has improved liquid repellency with respect to the functional liquid material 108 obtained by dispersing a silicon compound described later in a solvent. This aspect is shown in FIG.

As shown in FIG. 5A, on the substrate surface, oxygen atoms are bonded to hydrogen atoms to form OH groups. When an electron beam is irradiated in this state, hydrogen atoms are blown off by impact as shown in FIG. 5B, and the remaining oxygen atoms are in an electrically active radical state. When ethylbenzene gas is allowed to act on the surface in such a state, CF ₃ groups are generated as shown in FIG. 5C, and the liquid repellency of the region is improved.

  Next, as shown in FIG. 3C, the functional liquid material 108 obtained by dispersing the silicon compound as the functional material in the solvent is dropped into the first region 100 as in the first embodiment. . As described above, since the liquid repellent property of the second region 101 with respect to the functional liquid material 108 is improved, the functional liquid material 108 dropped on the first region 100 is the second region 101, that is, the first region 101. Outflow to the area around the first area 100 is suppressed.

  Next, as shown in FIG. 3D, as in the first embodiment, the solvent is dried and removed from the liquid material 108 dropped on the substrate 10 to obtain a thin film pattern 112 made of silicon fine particles. .

  Finally, as shown in FIG. 3E, the thin film pattern is irradiated with a laser beam 114, melted and recrystallized, and converted into a polycrystalline silicon film 116.

The pattern forming method of the present embodiment is characterized in that an electron beam is irradiated not on a region where a pattern is to be formed but on a region other than the region. Since the force to keep the dropped functional liquid material 108 within the range of the first region 100 always works, a higher definition pattern can be formed.
Further, since a liquid repellent surface is formed by bonding other molecules to the surface activated by generating oxygen radicals, a stable liquid repellent surface can be obtained even in an atmosphere with a low degree of vacuum. Therefore, a high-definition pattern can be formed with higher reproducibility.

(Electronic device manufacturing method)
Next, a method for manufacturing an electronic device according to the present invention will be described with reference to FIGS. FIGS. 6A to 6D, FIGS. 7A to 8D, FIGS. 8A to 8C, and FIGS. 9A to 9C are thin film transistors (hereinafter referred to as electronic devices). It is a schematic cross section showing a manufacturing process of “TFT”.

  First, as shown in FIG. 6A, an electron beam 206 is irradiated onto a second region 204 on the substrate 10 which is a region around the first region 202 where a TFT is to be formed. Hydrogen atoms bonded to the oxygen atoms 208 on the surface of the substrate 10 and / or electrons on the surface of the substrate 10 are blown off by the impact of electrons, and a dangling bond 210 is formed.

Next, as shown in FIG. 6B, the substrate 10 is left in the atmosphere of ethylbenzene gas 212 for a predetermined time. As described in the above-described pattern forming method embodiment, ethylbenzene gas is bonded to the dangling bond 210 to form the CF ₃ group 214. The CF ₃ group 214 has liquid repellency due to fluorine atoms. Therefore, the second region 204 has improved liquid repellency with respect to a liquid material in which at least a silicon compound solute described later is dispersed in a solvent.

  Next, as shown in FIG. 6C, a liquid material 216 in which a solute of a silicon compound is dispersed in a solvent is dropped from an inkjet head 218 into a first region 202 where a pattern is to be formed. The silicon compound and the solvent are preferably those described in the first embodiment of the pattern forming method.

Next, as shown in FIG. 6 (d), the liquid material 216 in which the solute of the silicon compound is dispersed in the solvent is heated to 100 ° C. to 200 ° C., and the solvent is dried and removed to form a thin film made of silicon fine particles. A pattern 220 is obtained.
The thin film pattern 220 can be formed with high definition by the effect of the dangling bond 210 described above, but the shape can be further adjusted using the electron beam 206. By irradiating the peripheral portion of the thin film pattern 220 with the electron beam 206, the shape can be adjusted (refined) in the direction of reducing the shape.

  Next, as shown in FIG. 7A, the thin film pattern 220 is melted and recrystallized by irradiating the thin film pattern 220 with a laser beam 222 and heated to obtain a polycrystalline silicon pattern 224 as a channel layer. The laser irradiation is preferably performed in an oxygen-free atmosphere as described in the first embodiment of the pattern forming method.

  Next, a silicon thin film is formed on the entire surface of the substrate 10. First, as shown in FIG. 7B, a liquid material 228 containing silicon fine particles is dropped onto a central portion of the substrate 10 from a nozzle 226 communicating with a liquid material supply source (not shown). Then, the liquid material 228 is spread over the entire surface of the substrate 10 by a spin coating method in which the substrate 10 is rotated and uniformly distributed, thereby forming a thin film of the liquid material 228 containing silicon fine particles. Since the liquid material is spread by centrifugal force, the liquid material 228 can be distributed in a substantially uniform thickness regardless of the difference in the properties of the surface of the substrate 10. Next, as shown in FIG. 7C, the entire substrate 10 is heated, and the solvent is dried and removed from the liquid material 228 containing silicon fine particles, thereby forming a silicon thin film 230.

  Next, as shown in FIG. 7D, the silicon thin film 230 is thermally oxidized by heating the substrate 10 to 1000 ° C. or more in an atmosphere containing oxygen molecules 232 to form a gate insulating film 234 made of a silicon oxide film. Form. In the case of WET oxidation (a technique of oxidizing by introducing water vapor obtained by burning hydrogen gas in an oxidation furnace), the heating temperature can be approximately 800 ° C.

  Next, as shown in FIG. 8A, a metal electrode such as tantalum is locally deposited at a substantially central portion on the polycrystalline silicon pattern 224 through a gate insulating film 234 to form a gate electrode 248. . The deposition is performed using a focused ion beam (hereinafter referred to as “FIB”).

  First, the substrate 10 is placed in a vacuum chamber (not shown), and a reaction gas (hereinafter referred to as “metal gas”) 242 containing metal atoms such as tantalum is introduced into the chamber. Then, FIB 244 using gallium ions is irradiated onto a region on the substrate 10 where the gate electrode is to be formed, that is, the substantially central portion on the polycrystalline silicon pattern 224 described above. The FIB 244 is obtained by applying a voltage to the needle-type liquid metal gallium 246. The metal gas 242 adsorbed on the substrate 10 is decomposed by the irradiation, and metal atoms 247 such as tantalum are deposited. As a result, the gate electrode 248 is formed in the region irradiated with the FIB 244, that is, in the substantially central portion on the polycrystalline silicon pattern 224.

Next, as shown in FIG. 8B, impurities such as phosphorus are ion-implanted into the polycrystalline silicon pattern 224 to form a source region 252 and a drain region 254. Ion implantation is also performed by FIB.
As shown in the figure, FIB 256 is extracted from needle-type phosphorus 250 instead of gallium as an ion source, and phosphorus ions are implanted into a predetermined region. Note that in this step, the gate electrode 248 functions as a mask for ion implantation.

  Next, an interlayer insulating film 260 is formed on the entire surface of the substrate 10 as shown in FIG. The formation method is the same as the formation of the gate insulating film 234 described above. That is, a liquid material 228 containing silicon fine particles is dropped onto the central portion of the substrate 10 (see FIG. 7B), and after the substrate 10 is rotated and uniformly distributed, the solvent is dried and removed to remove the silicon thin film. Get. Then, the silicon thin film is heated in an oxygen atmosphere to obtain an interlayer insulating film 260 made of a silicon oxide film.

Next, as shown in FIG. 9A, contact holes 262 are formed on the source region 252 and the drain region 254. The contact hole 262 is also formed using FIB. An FIB 264 obtained by applying a voltage to a needle-type liquid metal gallium 246 (not shown) is obtained. Then, by irradiating a predetermined region on the substrate 10 with the FIB 264, the interlayer insulating film 260 and the gate insulating film 234 are locally removed, and a contact hole 262 is formed. A part of the source region 252 and the drain region 254 is exposed by the contact hole 262, and conduction to the outside is possible.
Note that when the contact hole 262 is formed, a contact hole is preferably formed also on an extension of the tantalum (such as metal) layer that forms the gate electrode 248.

  Next, as shown in FIG. 9B, metal atoms such as Al are deposited in the contact hole 262 by FIB 278 to form a source electrode 272 and a drain electrode 274. Similarly to the formation of the gate electrode 248, the substrate 10 is placed in a vacuum chamber (not shown), and a metal gas 276 containing Al atoms is introduced into the chamber. Then, FIB 278 obtained by applying a voltage to the liquid metal gallium 246 is irradiated into the contact hole 262 to deposit Al atoms 277. Through the above steps, the TFT (thin film transistor) 290 as the electronic device described in the claims is formed on the substrate 10.

Finally, as shown in FIG. 9C, the probe needle 280 is brought into contact with the source electrode and the drain electrode. At the same time, a probe needle (not shown) is brought into contact with a contact hole (not shown) on the extension of the gate electrode 248 described above. Then, the electrical characteristics of the TFT 290 are measured.
With the above manufacturing method, the TFT 290 as an electronic device can be formed on the substrate 10 and the electrical characteristics can be measured. Since the thin film is formed or patterned using the FIB, it is not necessary to use a photomask or the like. As a result, the prototype of the electronic device and the evaluation of the prototype can be performed at a low cost and in a short time.

(Electronic device manufacturing equipment)
FIG. 10 is a schematic diagram of an electronic device manufacturing apparatus according to the first embodiment of the present invention. The manufacturing apparatus according to the present embodiment is mainly composed of a vacuum processing chamber 402 and a liquid material supply chamber 404 communicating with the vacuum processing chamber.

  The vacuum processing chamber 402 and the liquid material supply chamber 404 are connected by a transfer path 432, and the substrate 10 is transferred together with the substrate holding means 418 by a transfer rod 436 as a substrate transfer means in the transfer path 432. The conveyance path 432 is divided by a gate valve 434, and the degree of vacuum in the vacuum processing chamber 402 and the liquid material supply chamber 404 can be set independently. Therefore, the substrate 10 whose surface properties are changed in the vacuum processing chamber 402 can be transferred to the liquid material supply chamber 404 without being exposed to the atmosphere.

  The liquid material supply chamber 404 includes a substrate carry-in port 438 communicating with the outside. By opening and closing the loading port with the gate valve 434 closed, the substrate 10 can be loaded and unloaded in the manufacturing apparatus without affecting the atmosphere in the vacuum processing chamber 402.

The vacuum processing chamber 402 includes an ion source 412 as an energy beam irradiation means, an electron source 414, and a plurality of gas supply sources 416. The vacuum processing chamber 402 communicates with a vacuum pump (not shown), and the vacuum pump is closed with the gate valve 434 closed. Can be evacuated by operating.
Then, the substrate 10 held by the substrate holding means 418 can be irradiated with FIB and an electron beam from the ion source 412 and the electron source 414 to change the properties of the surface of the substrate 10.

Further, since the vacuum processing chamber 402 includes the gas supply source 416, the surface of the substrate 10 is stabilized and suitable for application of the liquid material by applying a gas after irradiating the substrate 10 with an electron beam or the like. Can be changed. As a result, a high-definition pattern can be formed on the substrate 10 with high reproducibility.
In the vacuum processing chamber 402, a thin film can be formed on the substrate 10. By irradiating the FIB while supplying gas from the gas supply source 416, a thin film can be deposited in an arbitrary region on the substrate 10.

  The liquid material supply chamber 404 includes an ink jet head 422 as a liquid material supply means that can be moved in the X direction and the Y direction by the driving means 426. A thin film pattern made of a material dispersed or dissolved in the liquid material by adding a step of dripping the liquid material 424 from the inkjet head 422 onto the substrate 10 held by the substrate holding means 418 and drying and removing the solvent. Can be formed.

  The liquid material supply chamber 404 communicates with a vacuum pump (not shown) similarly to the vacuum processing chamber 402, so that the pressure in the chamber can be lower than that in the atmosphere. It is also possible to control the gas species filling the room. Therefore, the liquid material 424 can be dropped from the inkjet head 422 while suppressing the change in the surface property of the substrate 10 in the vacuum processing chamber 402 from being caused by the atmosphere.

  In the present embodiment, the inkjet head 422 is used as the liquid material supply means for the substrate 10, but it is also possible to use a nozzle that supplies the liquid material only to the central portion of the substrate 10. When the nozzle is used as the liquid material supply means, a thin film can be formed on the entire surface of the substrate 10 by a so-called spin coating method, and then patterned in the vacuum processing chamber 402 with an electron beam.

  FIG. 11 shows a schematic diagram of an electronic device manufacturing apparatus according to a second embodiment of the present invention. The manufacturing apparatus according to the present embodiment is characterized in that a total of eight processing chambers each separated by a gate valve 434 are arranged on both sides of the transfer path 432. Each processing chamber is provided with a substrate holder 500, which can hold the substrate 10 and perform various processes. This apparatus corresponds to the manufacturing method of the TFT 290 described above, and each of the processing chambers can perform a part of the steps necessary for forming the TFT. By using all the processing chambers, the TFT 290 can be formed over the substrate 10 and further the electrical characteristics can be evaluated.

  Each processing chamber is provided with a transfer rod 436, and the substrate 10 can be transferred to and from the transfer path 432. The transfer path also includes a transfer rod 436, and the substrate 10 can be carried in or out from the substrate carry-in port 438. Each processing chamber has an exhaust port 437 communicating with a vacuum exhaust system (not shown), and the inside can be set to an arbitrary degree of vacuum. The function of each processing chamber is as follows.

  The first processing chamber A is a spin coating chamber. A rotation drive mechanism 502 that rotates the substrate holding unit 500 and a liquid material dropping nozzle 504 as a liquid material supply unit that can drop the liquid material at the center of the rotation are provided. A thin film made of the liquid material can be formed on the entire surface of the substrate 10 by dropping the liquid material while rotating the substrate 10. Note that the step of drying and removing the solvent (or dispersion medium) contained in the liquid material is performed separately.

  The second processing chamber B is an ink jet chamber. A liquid having an inkjet head 512 as liquid material supply means that can move in the X direction and the Y direction when the direction perpendicular to the substrate 10 is the Z direction, and having a functional material as a solute at an arbitrary position on the substrate 10 The material 514 can be dropped. Similar to the first processing chamber A, the step of drying and removing the solvent and the like contained in the liquid material is performed separately.

The third processing chamber C and the fourth processing chamber D are vacuum processing chambers. An ion source 522 that can irradiate FIB and an electron source 524 that can irradiate an electron beam are provided, and an arbitrary region on the surface of the substrate 10 can be irradiated. By the formation of dangling bonds (see FIG. 1 and the like) by the irradiation, the properties of the surface can be changed.
In addition, by providing a plurality of gas supply sources 526 and irradiating FIB while supplying gas, it is possible to perform processing such as ion implantation, etching, and thin film deposition on an arbitrary region on the surface of the substrate 10.

The fifth processing chamber E is a baking chamber. The interior of the chamber 10 can be heated by the heater 532 to heat the substrate 10 at an arbitrary temperature, and a process such as melt recrystallization of the thin film formed on the substrate 10 or drying and removal of the solvent can be performed.
Further, a gas supply source 526 is provided, and an arbitrary gas can be supplied during heating. For example, the silicon thin film on the substrate can be made into a silicon oxide film by heating while supplying oxygen gas, or the ion-implanted impurities can be activated by heating while supplying nitrogen gas.

  The sixth processing chamber F is a laser annealing chamber. By irradiating the thin film formed on the substrate 10 with a laser beam from the laser irradiation source 542, steps such as heating, processing, and crystallization can be performed. Therefore, a polycrystalline silicon layer or the like can be formed on the substrate by using another processing chamber in combination. Further, a micro Raman measurement apparatus can be provided in order to evaluate the crystallinity of the silicon layer.

  The seventh processing chamber G is an SEM chamber. An electron source 524 and a detector 552 are provided, and the appearance of the structure formed on the substrate can be observed using the first processing chamber to the sixth processing chamber.

  The eighth processing chamber H is a measurement chamber. A probe needle 562 that can be operated from the outside and a microscope 564 are provided, and the probe needle 562 is brought into contact with an electrode of an electronic device such as a TFT formed on the substrate using the first to sixth processing chambers. Can do. The probe needle 562 is connected to an electrical property evaluation device (not shown), and the electrical property of the electronic device formed on the substrate 10 can be measured from outside the device according to the present embodiment.

  As described above, the manufacturing apparatus according to the present embodiment can form an electronic device such as a TFT with only the apparatus and measure the electrical characteristics. Since each process is performed continuously, it is possible to manufacture and evaluate TFTs in a very short period of time. In addition, since the pattern is formed without using a photomask, the dimensions and the like can be easily corrected and changed. In addition, it is possible to observe the appearance of the substrate once carried into the apparatus without carrying it out to the outside, and further processing can be performed based on the result. Can be implemented. Therefore, by using this apparatus, manufacturing of electronic devices such as TFTs, in particular, trial manufacture and evaluation can be performed in a short period of time and at low cost, and development capability can be improved.

The figure which shows the pattern formation method concerning 1st Embodiment. The figure which shows the pattern formation method concerning 2nd Embodiment. The figure which shows the pattern formation method concerning 3rd Embodiment. The figure which shows the aspect of reaction of a dangling bond and ammonia gas. The figure which shows the aspect of reaction of a dangling bond and ethylbenzene gas. The schematic cross section which shows the manufacturing process of TFT. The schematic cross section which shows the manufacturing process of TFT. The schematic cross section which shows the manufacturing process of TFT. The schematic cross section which shows the manufacturing process of TFT. The schematic diagram which shows the manufacturing apparatus of the electronic device concerning the 1st Embodiment of this invention. The schematic diagram which shows the manufacturing apparatus of the electronic device concerning the 2nd Embodiment of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 ... Board | substrate, 100 ... 1st area | region, 101 ... 2nd area | region, 102 ... Dangling bond, 104 ... Oxygen atom, 106 ... Electron beam, 108 ... Functional liquid material, 110 ... Nozzle, 112 ... Thin film pattern, 114 ... laser beam, 116 ... polycrystalline silicon film, 120 ... NH ₃ gas, 122 ... NH group, 126 ... ethylbenzene gas, 128 ... CF ₃ group, 202 ... first region, 204 ... second region, 206 ... Electron beam, 208... Oxygen atom, 210... Dangling bond, 212... Ethylbenzene gas, 214... CF ₃ group, 216... Liquid material in which solute of silicon compound is dispersed in solvent. ... laser beam, 224 ... polycrystalline silicon pattern, 226 ... nozzle, 228 ... contains silicon fine particles Material: 230 ... Silicon thin film, 232 ... Oxygen molecule, 234 ... Gate insulating film, 242 ... Metal gas, 244 ... FIB, 246 ... Liquid metal gallium, 247 ... Metal atom, 248 ... Gate electrode, 250 ... Phosphorus, 252 ... Source Region, 254 ... drain region, 260 ... interlayer insulating film, 262 ... contact hole, 264 ... FIB, 272 ... source electrode, 274 ... drain electrode, 276 ... metal gas, 277 ... Al atom, 278 ... FIB, 280 ... probe needle 290 ... TFT, 402 ... vacuum processing chamber, 404 ... liquid material supply chamber, 412 ... ion source, 414 ... electron source, 416 ... gas supply source, 418 ... substrate holding means, 422 ... inkjet head, 424 ... liquid material, 426 ... Driving means, 432 ... Conveying path, 434 ... Gate valve, 436 ... Transfer rod, 437 Exhaust port, 438 ... Substrate carry-in port, 500 ... Substrate holder, 502 ... Rotary drive mechanism, 504 ... Liquid material dropping nozzle, 512 ... Inkjet head, 514 ... Liquid material, 522 ... Ion source, 524 ... Electron source, 526 ... Gas supply source, 532 ... heater, 542 ... laser irradiation source, 552 ... detector, 562 ... probe needle, 564 ... microscope, A ... first processing chamber, B ... second processing chamber, C ... third processing Chamber, D ... fourth processing chamber, E ... fifth processing chamber, F ... sixth processing chamber, G ... seventh processing chamber, H ... eighth processing chamber.

Claims (20)

A vacuum processing chamber including therein an energy beam irradiation unit, a first gas exhaust unit, and a first substrate holding unit capable of holding a substrate;
A liquid that includes a first gas supply unit, a second gas exhaust unit, and a second substrate holding unit capable of holding the substrate, and that supplies a liquid material onto the substrate held by the second substrate holding unit; A liquid material supply chamber comprising material supply means;
A transfer path communicating between the vacuum processing chamber and the liquid material supply chamber;
A first gate valve for opening and closing the conveyance path;
Transport means capable of transporting the substrate between the vacuum processing chamber and the liquid material supply chamber;
A substrate carry-in port communicating with at least one of the vacuum processing chamber and the liquid material supply chamber;
An apparatus for manufacturing an electronic device, comprising:   The apparatus for manufacturing an electronic device according to claim 1, wherein the energy beam is a first electron beam.   The apparatus for manufacturing an electronic device according to claim 1, wherein the vacuum processing chamber includes a gas supply source.   The said energy beam is a focused ion beam, The manufacturing apparatus of the electronic device of any one of Claims 1-3 characterized by the above-mentioned.   At least the laser beam irradiation means, the third gas exhaust means, and the third substrate holding means capable of holding the substrate, and further comprising a laser annealing chamber communicating with the transfer path via a second gate valve. The apparatus for manufacturing an electronic device according to claim 1, wherein:   At least a heating means, a second gas supply means, a fourth gas exhaust means, and a fourth substrate holding means capable of holding the substrate; and further comprising a heating chamber communicating with the transfer path via a third gate valve The apparatus for manufacturing an electronic device according to claim 1, further comprising:   An electron beam irradiation means capable of generating a second electron beam and irradiating the substrate with the second electron beam, and detecting a third electron beam generated by reflecting the irradiated second electron beam on the substrate An electronic device manufacturing apparatus according to any one of claims 1 to 5, further comprising an electron microscope chamber including a detecting unit.   A probe needle that is electrically connected to an external measuring instrument and can contact a predetermined portion on the substrate; and fifth substrate holding means that can hold the substrate; and the transport path and the fourth gate valve. The apparatus for manufacturing an electronic device according to claim 1, further comprising a nanoprobe chamber communicating with each other. An irradiation step of irradiating the first region on the substrate with an energy beam to form a dangling bond;
A liquid material dropping step of dropping a liquid material containing a functional material and a solvent in the first region;
Have
Between the irradiation process and the liquid material dropping process, the substrate is held in a controlled atmosphere without being exposed to the atmosphere. An irradiation step of irradiating the first region on the substrate with an energy beam to form a dangling bond;
By supplying a gas having a property of forming a lyophilic surface by bonding with the dangling bond, the lyophilicity of the first region with respect to a liquid material containing a functional material and a solvent is increased. A gas treatment process;
A dropping step of dropping the liquid material into the first region;
Including
The pattern forming method, wherein the substrate is held in a controlled atmosphere without being exposed to the atmosphere between the irradiation step and the gas treatment step, and between the gas treatment step and the dropping step. An irradiation step of irradiating an energy beam to a second region, which is a region other than the first region, on the substrate to form a dangling bond;
By supplying a gas having a property of forming a liquid-repellent surface by bonding with the dangling bond, the liquid repellency of the second region with respect to a liquid material containing a functional material and a solvent is increased. A gas treatment process;
A dropping step of dropping the liquid material into the first region;
Including
The pattern forming method, wherein the substrate is held in a controlled atmosphere without being exposed to the atmosphere between the irradiation step and the gas treatment step, and between the gas treatment step and the dropping step. An irradiation step of irradiating the first region on the substrate with an energy beam to form a dangling bond;
A thin film forming step of forming a thin film containing the functional material by dropping the solvent after dropping a liquid material containing the functional material and the solvent in the first region;
Have
Between the irradiation process and the thin film formation process, the substrate is held in a controlled atmosphere without being exposed to the atmosphere. An irradiation step of irradiating the first region on the substrate with an energy beam to form a dangling bond;
By combining with the dangling bond and supplying a gas having a property of forming a lyophilic surface by the bonding, the lyophilicity of the first region with respect to a liquid material containing a functional material and a solvent is increased. Enhanced gas treatment process;
A thin film forming step of forming the thin film containing the functional material by removing the solvent after dropping the liquid material in the first region;
Have
An electronic device characterized in that the substrate is held in a controlled atmosphere without being exposed to the atmosphere between the irradiation step and the gas treatment step and between the gas treatment step and the thin film formation step. Production method. An irradiation step of irradiating an energy beam to a second region, which is a region other than the first region, on the substrate to form a dangling bond;
The gas for the liquid material containing the functional material and the solvent is supplied by supplying a gas that does not react with the material forming the substrate and is bonded to the dangling bond to make the surface liquid-repellent. A gas treatment step for increasing the liquid repellency of the region 2;
A gas treatment step of increasing the liquid repellency of the second region with respect to the liquid material by supplying a gas having a property of forming a liquid repellent surface by the bonding with the dangling bond;
A thin film forming step of forming the thin film containing the functional material by removing the solvent after dropping the liquid material in the first region;
Have
An electronic device characterized in that the substrate is held in a controlled atmosphere without being exposed to the atmosphere between the irradiation step and the gas treatment step and between the gas treatment step and the thin film formation step. Production method.   15. The refinement process according to claim 12, further comprising a refining step of shaping the peripheral edge by irradiating a peripheral edge of the thin film with a focused ion beam after the thin film forming process. A method for manufacturing an electronic device.   16. The method for manufacturing an electronic device according to claim 12, wherein the functional material is silicon, and the thin film is a silicon layer.   The method of manufacturing an electronic device according to claim 16, further comprising a step of crystallizing the silicon layer by irradiating a laser beam.   18. The method according to claim 17, further comprising: forming a silicon oxide film by applying a liquid material containing at least silicon on the substrate on which the gate electrode is formed, and solidifying and oxidizing the liquid material. A method for manufacturing an electronic device.   The method further includes the step of forming a gate electrode by locally laminating a conductive material on the channel layer, which is a part of the silicon layer, via the silicon oxide film using a focused ion beam. The method for manufacturing an electronic device according to claim 18. Removing a part of the interlayer insulating film locally using a focused ion beam and forming a contact hole in a region not overlapping the gate electrode on the channel layer;
Filling the contact hole with a conductive material to form a source electrode and a drain electrode;
The method of manufacturing an electronic device according to claim 19, further comprising:

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