KR102277446B1 - Method for forming a three dimensional structure - Google Patents

Abstract

The present invention relates to a method of forming a silicon-based three-dimensional structure through a solution process, and more particularly, to provide an organic silicon precursor on a substrate to form an organic silicon pattern; and irradiating ultraviolet light to the organic silicon pattern to form a silicon oxide pattern. In this case, the organic silicon precursor may ^{have a viscosity of 1.0 cP to 1.0×10 7} cP under 20° C. and 1 atmosphere, and the organic silicon pattern and the silicon oxide pattern may have substantially the same size.

Description

Method for forming a three-dimensional structure {Method for forming a three dimensional structure}

The present invention relates to a method of forming a silicon-based three-dimensional structure through a solution process.

Recently, research and development of flexible materials/devices are being actively conducted. Various metal/insulator/semiconductor materials are being applied to plastic substrates with flexibility beyond the limitations of substrates such as silicon and glass. In particular, in the case of silicon-based materials, various materials in a solution state are being developed. In the case of such a solution-state silicon-based material, it shows reliable electrical/mechanical/optical properties, so it has the advantage of being applicable to various platform-based application technologies such as next-generation displays, portable devices, solar cells, and bio/medical products. and has excellent applicability.

However, the conventional silicone-based material in a solution state can be used as a coating agent or a mold by firing at a low temperature. In this case, although flexibility is maintained, low density and poor heat resistance have problems. _{Meanwhile, in order to obtain a stable material such as SiO 2} from a silicon-based material in a solution state, a non-vacuum process such as high-temperature firing or plasma treatment is required. However, since a flexible substrate material such as plastic requires a low-temperature process, it is necessary to develop a process capable of forming a silicon thin film/structure having high density and excellent heat resistance even in a low-temperature process. Currently, the inorganic thin film process using a low-temperature process is representative of forming a dense dielectric/protective film using the ALD method, but the deposition rate is slower than that of the non-vacuum-based process, so there is a problem of low yield. To overcome this, research on depositing a thin film in the form of an organic-inorganic composite is being conducted, but in the case of an organic material, there is a problem in that properties such as permeability/heat resistance/chemical resistance are poorer than that of an inorganic material.
The technology underlying the present invention is disclosed in Korean Patent Application Laid-Open No. 10-2012-0106359 (2012.09.26).

The technical problem to be achieved by the present invention is to provide a method of forming a high-density three-dimensional silicon structure even in the process of room temperature and pressure.

According to a concept of the present invention, a method for forming a three-dimensional structure includes: providing an organic silicon precursor on a substrate to form an organic silicon pattern; and irradiating ultraviolet light to the organic silicon pattern to form a silicon oxide pattern. In this case, the organic silicon precursor may ^{have a viscosity of 1.0 cP to 1.0×10 7} cP under 20° C. and 1 atmosphere, and the organic silicon pattern and the silicon oxide pattern may have substantially the same size.

The organosilicon precursor is in a liquid state at 20° C. and 1 atm, and the organosilicon precursor may include a Si—O bond.

The organosilicon precursor may include polydimethylsiloxane (PDMS) or tetraethylorthosilicate (TEOS).

The ultraviolet light may have a wavelength range of 100 nm to 200 nm.

Irradiating the ultraviolet light may be performed simultaneously with providing the organosilicon precursor on the substrate or after forming the organosilicon pattern.

The organosilicon precursor may further include a solvent or ion capable of changing its viscosity and electrical conductivity. Providing the organosilicon precursor on the substrate includes using an electrohydrodynamic jet printing method, and the solvent is cyclopentanone, cyclohexanone, gamma-butyrolactone. (γ-butyrolactone), toluene, methanol, ethanol, ethyl ether, N,N-dimethyl acetamide, N-methyl-2-pyrrodinone, tetra with tetrahydrofuran, ethyl acetate and hexane, glycerol, Triethylene Glycol Monomethyl Ether, Ethylene glycol and Propylene glycol At least one selected from the group consisting of, the ion may include an acid, a base, or an ionic salt.

Providing the organic silicon precursor on the substrate may include further using a jet printing method or an imprint lithography method.

The organic silicon pattern and the silicon oxide pattern may have an aspect ratio of 1 to 10.

The organic silicon pattern and the silicon oxide pattern are provided in plurality, respectively, and forming the organic silicon patterns and the silicon oxide patterns may include: forming a first silicon oxide pattern from a first organic silicon pattern; and forming a second silicon oxide pattern from a second organic silicon pattern, wherein the second silicon oxide pattern may be formed on the first silicon oxide pattern.

The second organosilicon pattern may be formed on the first organosilicon pattern, and the first and second silicon oxide patterns may be formed together by irradiating ultraviolet rays to the stacked first and second organosilicon patterns. have.

Forming the organosilicon pattern includes forming the organosilicon pattern having a lattice shape on the substrate in a plan view, and forming the silicon oxide pattern includes irradiating ultraviolet rays to the organosilicon pattern to form a lattice It may include forming the silicon oxide pattern of the form.

According to another concept of the present invention, a method for forming a three-dimensional structure includes: providing an organic silicon precursor on a substrate to form an organic silicon pattern; and irradiating the organic silicon pattern with ultraviolet rays having a wavelength range of 100 nm to 200 nm to form a silicon oxide pattern. In this case, the organic silicon precursor may be in a liquid state ^{including a Si-O bond and having a viscosity of 1.0 cP to 1.0×10 7 Cp at 20° C. and 1 atm.}

The organosilicon precursor may include polydimethylsiloxane (PDMS) or tetraethylorthosilicate (TEOS).

Forming the organosilicon pattern includes forming sequentially stacked organosilicon patterns, and forming the silicon oxide pattern includes irradiating ultraviolet light to the organosilicon patterns to sequentially stack silicon oxide patterns. may include forming.

The method of forming a three-dimensional structure according to the present invention can form a silicon oxide structure having a chemical structure similar to that of _{SiO 2 or similar thereto without any surface treatment or additives under room temperature and pressure.} Accordingly, it is possible to minimize damage to the substrate on which the three-dimensional structure is to be formed and other thin films. Furthermore, it is possible to form a more complex three-dimensional structure using a high-viscosity organosilicon solution.

1A to 1C are cross-sectional views schematically illustrating a method of forming a three-dimensional structure according to an embodiment of the present invention.
2 is a graph analyzing the atomic composition of a silicon oxide pattern formed according to embodiments of the present invention.
3 and 4 are cross-sectional views schematically showing a three-dimensional structure according to other embodiments of the present invention.
5 is a schematic view showing an electrohydrodynamic jet printing apparatus for forming an organic silicon pattern according to embodiments of the present invention.
6A, 6B, and 7 are cross-sectional views schematically illustrating a method of forming an organic silicon pattern using an electrohydrodynamic jet printing apparatus.
8A to 8C are perspective views schematically illustrating a method of forming a semiconductor device according to another exemplary embodiment of the present invention.

In order to fully understand the configuration and effect of the present invention, preferred embodiments of the present invention will be described with reference to the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, and may be implemented in various forms and various modifications may be made. However, it is provided so that the disclosure of the present invention is complete through the description of the present embodiments, and to fully inform those of ordinary skill in the art to which the present invention belongs, the scope of the invention.

In this specification, when a component is referred to as being on another component, it means that it may be directly formed on the other component or a third component may be interposed therebetween. In addition, in the drawings, the thickness of the components is exaggerated for effective description of the technical content. Parts indicated with like reference numerals throughout the specification indicate like elements.

Embodiments described herein will be described with reference to cross-sectional and/or plan views that are ideal illustrative views of the present invention. In the drawings, thicknesses of films and regions are exaggerated for effective description of technical content. Accordingly, the regions illustrated in the drawings have a schematic nature, and the shapes of the regions illustrated in the drawings are intended to illustrate specific shapes of regions of the device and not to limit the scope of the invention. In various embodiments of the present specification, terms such as first, second, third, etc. are used to describe various components, but these components should not be limited by these terms. These terms are only used to distinguish one component from another. The embodiments described and illustrated herein also include complementary embodiments thereof.

The terminology used herein is for the purpose of describing the embodiments and is not intended to limit the present invention. As used herein, the singular also includes the plural unless specifically stated otherwise in the phrase. As used herein, the terms 'comprises' and/or 'comprising' do not exclude the presence or addition of one or more other components.

Example One

1A to 1C are cross-sectional views schematically illustrating a method of forming a three-dimensional structure according to an embodiment of the present invention.

Referring to FIG. 1A , by providing an organic silicon precursor on a substrate 100 , an organic silicon pattern 110 may be formed. The substrate 100 may be a semiconductor substrate such as a silicon substrate, a transparent substrate such as a glass substrate, or a flexible substrate such as a polymer substrate, but is not particularly limited. To provide the organic silicon precursor on the substrate 100 , an electrohydrodynamic jet printing method, a jet printing method, an imprint lithography method, or a combination thereof may be used, but is not particularly limited. A specific method of providing the organic silicon precursor will be described later.

The organosilicon precursor may include a compound having a Si—O bond. The organosilicon precursor may be a material capable of forming a _{silicon oxide (SiO 2} ) by curing when ultraviolet rays are irradiated thereto. In addition, the organic silicon precursor may be a material in a liquid state under 20 ℃ and 1 atmosphere. For example, the organic silicon precursor may include polydimethylsiloxane (PDMS) or tetraethylorthosilicate (TEOS).

The organosilicon precursor may have various viscosities, vaporization temperatures, electrical conductivity, and the like even with the same material. For example, when the organosilicon precursor is the polydimethylsiloxane (PDMS), the PDMS may have various viscosity ranges and vaporization temperatures depending on the molecular weight thereof and the type of monomolecules to be mixed. For example, the PDMS may have a viscosity range of 1 cP to 1.0×10 ^{7 cP at 20° C. and 1 atm.}

Furthermore, the organic silicon precursor may further include a solvent and/or ions, thereby variously changing its viscosity, vaporization temperature, and electrical conductivity. The solvent is, for example, cyclopentanone, cyclohexanone, gamma-butyrolactone, toluene, methanol, ethanol, ethyl ether, N,N-dimethyl acetamide ( N,N-dimethyl acetamide), N-methyl-2-pyrrodinone, tetrahydrofuran, ethyl acetate and hexane, glycerol, It may include at least one selected from the group consisting of triethylene glycol monomethyl ether, ethylene glycol, and propylene glycol. In order to control the electrical conductivity of the solution containing the organosilicon precursor, an acid (eg, HCl, HNO3, CH3COOH, etc.), a base (eg, KOH, NaOH, NH4OH, etc.) or an ionic salt (eg, , NaCl, KCl, etc.) can be added. If the electrohydrodynamic jet printing method is used, the process may be optimized by adjusting the viscosity and electrical conductivity of the organic silicon precursor, and a detailed description thereof will be given later.

Optionally, the organic silicon precursor may not include additives such as a crosslinking agent for thermal curing or a photoinitiator for photocuring. The organosilicon precursor may be rapidly cured through ultraviolet rays in a specific wavelength range, and a detailed description thereof will be described later.

The organic silicon pattern 110 formed on the substrate 100 may have a shape such as a thin film, a line shape, a bar shape, or an uneven shape, but may be formed according to a structure desired by those skilled in the art. If the organosilicon precursor has a high viscosity of 1.0 cP to 1.0×10 ⁷ cP under 20° C. and 1 atm, the organosilicon pattern 110 may be cured while maintaining the shape when initially formed. Therefore, it may be more advantageous to form a three-dimensional structure according to the present invention.

Referring to FIG. 1B , ultraviolet 125 may be irradiated to the organic silicon pattern 110 formed on the substrate 100 . The UV 125 may be irradiated through the UV irradiator 120 . The ultraviolet irradiator 120 may include a large-area light source of a lamp type or a direct light source such as an LED or a laser. The ultraviolet ray 125 may have a wavelength range of 100 nm to 200 nm.

FIG. 2 is a graph analyzing the atomic composition of the organic silicon pattern 110 (PDMS) after irradiating ultraviolet rays 125 having a wavelength range of 100 nm to 200 nm for 1 minute.

Referring to FIG. 2 , the horizontal axis represents an etching time, that is, a depth of an object. The atomic composition of the organic silicon pattern 110 was analyzed until the etching time of 200 seconds, and it can be seen that oxygen atoms are about twice that of silicon atoms. That is, it can be confirmed that the organic silicon pattern 110 (eg, PDMS) according to the present invention _{can be converted into silicon oxide (SiO 2 ) through ultraviolet 125 irradiation having a wavelength range of 100 nm to 200 nm.} . After the etching time is around 200 seconds, it corresponds to the substrate 100 .

That is, by using the ultraviolet 125 wavelength of 100 nm to 200 nm through the experimental results, the organic silicon pattern 110 according to the present invention is cured in a short time without an additional crosslinking agent or photoinitiator It can be confirmed that it can be converted into silicon oxide. can This is because the organic silicon pattern 110 can well absorb the ultraviolet ray 125 in the wavelength range. Furthermore, since the irradiation of the ultraviolet rays 125 can be performed at room temperature (about 20° C.) and under normal pressure (about 1 atmosphere), damage to the substrate 100 and the organic silicon pattern 110 can be minimized. .

As the ultraviolet ray 125 , a vacuum UV or a deep UV laser such as a KrF or ArF laser may be used. In the case of using the deep ultraviolet laser, since the intensity of light is very strong compared to a general ultraviolet lamp, the reaction time (curing time) can be greatly shortened. In addition, since only an area corresponding to the size of the focused laser beam can be selectively scanned, laser-based micro-patterning may be possible. For example, although not shown, when the organic silicon pattern 110 is formed in the form of a thin film, the laser beam may be scanned only on a portion of the thin film to be patterned such that only the part of the thin film is converted into silicon oxide. Furthermore, if a pulsed laser is used, since the scan time is very short, thermal diffusion hardly occurs around the scan region, so that only the region to be reacted can be selectively changed to silicon oxide.

Referring to FIG. 1C , the organic silicon pattern 110 may be cured to form a silicon oxide pattern 130 . The shape of the silicon oxide pattern 130 may correspond to the shape of the organic silicon pattern 110 previously formed on the substrate 100 . In addition, as described above, through ultraviolet irradiation in a specific range, the silicon oxide pattern 130 may have SiO ₂ or a chemical structure similar thereto. _{Furthermore, since the silicon oxide pattern 130 having SiO 2} or a chemical structure similar thereto can be formed without any surface treatment or additives, the process can be simplified.

Although an exemplary method of forming a three-dimensional structure of a simple shape has been described in this embodiment, a more complex three-dimensional pattern (structure) can be formed using the organosilicon precursor having a high viscosity, and alternatively, the organosilicon A complex three-dimensional pattern (structure) may be formed by stacking a plurality of the pattern 110 or the salicone oxide pattern. In particular, the latter will be described next.

Example 2

3 and 4 are cross-sectional views schematically showing a three-dimensional structure according to other embodiments of the present invention. In the present embodiments, detailed descriptions of technical features overlapping with those previously described with reference to FIGS. 1A to 1C will be omitted, and differences will be described in detail. The same reference numbers may be provided for the same configuration as the manufacturing method of the three-dimensional structure for explaining the concept of the present invention above.

Referring to FIG. 3 according to an embodiment of the present invention, a silicon oxide structure SS may be provided on the substrate 100 . The silicon oxide structure SS may include first and second silicon oxide patterns 130a and 130b sequentially stacked on the substrate 100 . Although not shown, in a plan view, the second silicon oxide pattern 130b may overlap the first silicon oxide pattern 130a. However, as another example, the second silicon oxide pattern 130b may cross the first silicon oxide pattern 130a, and thus only a part of the second silicon oxide pattern 130b is the first silicon oxide pattern 130a. ) can be overlapped with a part of In conclusion, the arrangement relationship of the first and second silicon oxide patterns 130a and 130b is not particularly limited, and may be variously changed according to the specific use of the semiconductor device.

As a method of forming the silicon oxide structure SS, there may be two examples. For example, the first silicon oxide pattern 130a may be formed on the substrate 100 according to the method described above with reference to FIGS. 1A to 1C . Thereafter, the second silicon oxide pattern 130b may be formed on the first silicon oxide pattern 130a according to the method described with reference to FIGS. 1A to 1C again.

As another example, first and second organic silicon patterns (not shown) sequentially stacked on the substrate 100 may be formed. Forming each of the first and second organic silicon patterns may be the same as described above with reference to FIG. 1A . In particular, when an organic silicon precursor having a high viscosity (eg, 1.0 ^{cP to 1.0 × 10 7} cP) is used, the shape of the organic silicon pattern can be maintained even before curing as described above. Accordingly, after forming the first organosilicon pattern, a second organosilicon pattern may be formed directly on the first organosilicon pattern.

Then, by irradiating ultraviolet rays to the stacked first and second organic silicon patterns, the stacked first and second silicon oxide patterns 130a and 130b may be respectively formed. In the case of this example, since the silicon oxide structure SS can be formed by one UV irradiation compared to the example described above, a more efficient process can be performed.

Referring to FIG. 4 according to another embodiment of the present invention, a silicon oxide structure SS may be provided on the substrate 100 . The silicon oxide structure SS may include first to fourth silicon oxide patterns 130a , 130b , 130c , and 130d sequentially stacked on the substrate 100 . Although not shown, in a plan view, the first to fourth silicon oxide patterns 130a, 130b, 130c, and 130d may overlap each other. However, the arrangement relationship of the first to fourth silicon oxide patterns 130a, 130b, 130c, and 130d is not particularly limited, and may be variously changed according to the specific use of the semiconductor device.

For example, the silicon oxide structure SS may have a columnar shape in which a plurality of the silicon oxide patterns 130a to 130d are stacked. Since the silicon oxide structure SS according to the present invention can easily repeatedly stack the plurality of silicon oxide patterns 130a to 130d, a three-dimensional structure having a high aspect ratio can be implemented. For example, the silicon oxide structure SS may have a width A and a height B. In this case, the aspect ratio (B/A) of the silicon oxide structure SS may be in the range of 1 to 10.

As a method of forming the silicon oxide structure SS, as described above with reference to FIG. 3 , there may be two examples. For example, the first to fourth silicon oxide patterns 130a, 130b, 130c, and 130d may be independently formed according to the method described above with reference to FIGS. 1A to 1C .

As another example, after sequentially stacked first to fourth organosilicon patterns (not shown) are formed using an organosilicon precursor having a high viscosity, the first to fourth organosilicon patterns are irradiated with ultraviolet light to First to fourth silicon oxide patterns 130a, 130b, 130c, and 130d may be formed, respectively.

Example 3

5 is a schematic view showing an electrohydrodynamic jet printing apparatus for forming the organic silicon pattern 110 according to embodiments of the present invention.

Referring to FIG. 5 , the electrohydrodynamic jet printing apparatus may include a stage 200 on which a substrate 100 is loaded. The stage 200 may include a moving part 201 located at the lowest end, a metal plate 203 on the moving part 201 , and a heater 205 on the metal plate 203 . The moving unit 201 may move two-dimensionally or three-dimensionally. That is, the moving unit 201 may move the substrate 100 to form a pattern on the substrate 100 . The metal plate 203 serves as a support, and the heater 205 may heat the substrate 100 to a predetermined temperature.

The electrohydrodynamic jet printing apparatus may include a spraying unit 210 for discharging the organic silicon precursor 115 . The injection unit 210 may include a body 213 and a nozzle 211 . The organic silicon precursor 115 introduced into the body 213 may move to the nozzle 211 through a movement passage in the body 213 . Thereafter, the organic silicon precursor 115 may be discharged from the nozzle 211 by an electric field between the nozzle 211 and the substrate 100 . The discharged organic silicon precursor 117 may be provided on the substrate 100 . A specific principle for this will be described later.

The electrohydrodynamic jet printing apparatus may include a syringe pump 220 for supplying the organosilicon precursor 115 in a liquid state to the injection unit 210 . Specifically, the syringe pump 220 may include a cylinder 221 , a piston 223 , and a driving unit 225 . The organosilicon precursor 115 may be filled in the cylinder 221 . As the piston 223 rises by the driving unit 225 , the organic silicon precursor 115 in the cylinder 221 may be transferred to the injection unit 210 .

The electrohydrodynamic jet printing apparatus may include a power supply 230 and a control unit 240 . The power supply 230 may be electrically connected to the stage 200 and the injection unit 210 . Accordingly, the power supply 230 may generate a potential difference between the substrate 100 of the stage 200 and the nozzle 211 of the spray unit 210 to form an electric field therebetween. A more detailed description thereof will be given later.

The control unit 240 may be connected to the stage 200 , the syringe pump 220 , and the power supply 230 , respectively, and control them. For example, the control unit 240 may be connected to the moving unit 201 of the stage 200 to control the movement of the substrate 100 for forming a pattern. The control unit 240 may be connected to the syringe pump 220 to control the flow rate and conveying pressure of the organic silicon precursor 115 transferred from the syringe pump 220 . The controller 240 may be connected to the power supply 230 to adjust an electric field between the substrate 100 and the nozzle 211 . The control unit 240 may be, for example, a computer.

6A, 6B, and 7 are cross-sectional views schematically illustrating a method of forming the organic silicon pattern 110 using the electrohydrodynamic jet printing apparatus described with reference to FIG. 5 .

Referring to FIG. 6A , the organic silicon precursor 115 may be discharged by an electrohydrodynamic method through the nozzle 211 to form the organic silicon pattern 110 on the substrate 100 .

Electrohydrodynamic jet printing is a technique for discharging droplets using an electric field. When a predetermined voltage is applied between the substrate 100 and the nozzle 211 , an electric field EF may be generated therebetween. At the same time, charges may be concentrated on the surface of the organic silicon precursor 115 near the nozzle 211 . In this case, an electrostatic attraction may be generated by the electric charge generated on the surface and the electric field EF, and the organic silicon precursor 115 may be discharged through the nozzle 211 due to the attractive force.

The discharged organic silicon precursor 117 may have various drop sizes. For example, the drop size may be adjusted by the electrostatic attraction. Since the electrostatic attraction depends on the electrical conductivity, viscosity, and strength of the electric field EF of the organosilicon precursor 115 , the desired drop size may be formed by appropriately adjusting the parameters. For example, a fine pattern may be formed by discharging droplets having a size smaller than the size of the nozzle 211 by controlling the electrostatic attraction, which will be described later in detail (see FIG. 7 ).

Since the electrohydrodynamic jet printing method does not need to form a pattern by applying pressure on the substrate 100 like screen printing, physical damage to the substrate 100 can be minimized. In addition, if the general jet printing method is a concept of pushing and jetting droplets, the electrohydrodynamic jet printing method pulls the droplets using the potential difference between the nozzle 211 and the substrate 100 . The concept of ejection. Accordingly, since the electrohydrodynamic jet printing method is not significantly affected by the viscosity of the organosilicon precursor 115 , it is possible to discharge the organosilicon precursor 115 of various viscosities (particularly, high viscosity).

Referring to FIG. 6B , the organic silicon precursor 115 may be discharged by an electrohydrodynamic method through the nozzle 211 to form the organic silicon patterns 110 having concavo-convex shapes on the substrate 100 . That is, unlike in FIG. 6A , as the discharged organic silicon precursor 115 is discontinuously provided on the substrate 100 , drop-shaped patterns may be formed. This can be implemented by controlling the discharge of the organic silicon precursor 115 by controlling the electrostatic attraction described above. Through the organic silicon patterns 110 in the concavo-convex shape, it is possible to implement a three-dimensional structure of more various shapes.

Referring to FIG. 7 , unlike FIG. 6A , the organic silicon precursor 115 may be discharged in the form of a cone jet. That is, a drop size of the discharged organic silicon precursor 117 may be smaller than a size of the nozzle 211 .

Specifically, when the discharge pressure of the organosilicon precursor 115 due to electrostatic attraction is greater than the surface tension of the organosilicon precursor 115, the spherical surface of the organosilicon precursor 115 becomes a cone. can be transformed into the form of In addition, droplets having a drop size smaller than the drop size shown in FIG. 6A (ie, 1/10 or less of the nozzle 211 size) may be discharged. The discharged organic silicon precursor 117 may be sprayed in the form of a realt or a spray. The organic silicon pattern 110 formed using the cone jet may have a line width of several tens of μm and a height of several μm. That is, by using the electrohydrodynamic jet printing method, a fine pattern can be directly formed by printing technology even when the organic silicon precursor 115 having a high viscosity (eg, 1.0 cP to 1.0 × 10 ^{7 cP) is used.} can

The electrohydrodynamic jet printing method described above with reference to FIGS. 6A, 6B and 7 can be easily combined with other thin film forming processes. For example, although not shown, a thin film is formed on the substrate 100 by a method such as chemical vapor deposition, spin coating, sputtering, or electroplating, and then on the thin film using the electrohydrodynamic jet printing method. An organic silicon pattern 110 may be formed. Accordingly, in the process of forming the semiconductor device, the three-dimensional silicon oxide structure SS can be easily formed on any thin film.

Example 4

8A to 8C are perspective views schematically illustrating a method of forming a semiconductor device according to another exemplary embodiment of the present invention. More specifically, the semiconductor device may be a liquid crystal display. In the present embodiment, detailed descriptions of technical features overlapping with those previously described with reference to FIGS. 1A to 1C will be omitted, and differences will be described in detail.

Referring to FIG. 8A , a lower substrate 300 may be provided. The lower substrate 300 may be a transparent substrate, for example a glass or plastic substrate.

A reflective plate 305 may be provided under the lower substrate 300 . For example, the reflection plate 305 may include a white plate, a mirror image, or a luminance enhancement film (DBEF). For example, when the reflective plate 305 is used, a reflective guest host type liquid crystal display device may be implemented. In another embodiment, the reflection plate 305 may be provided between the lower substrate 300 and the first electrode layer 310 to be described later, but is not particularly limited.

The first electrode layer 310 may be formed on the lower substrate 300 . Although not shown, the first electrode layer 310 may be provided in plurality and may be arranged to be horizontally spaced apart from each other. For example, the first electrode layer 310 may include indium tin oxide (ITO), indium zinc oxide (IZO), silver nanowires, carbon nanotubes, graphene, PEDOT:PSS, polyaniline, polythiophene, or a combination thereof. may include

A first insulating layer 320 may be formed on the first electrode layer 310 . The first insulating layer 320 may short-circuit the liquid crystal layer 335 , which will be described later, from the first electrode layer 310 . In addition, the first insulating layer 320 may control the alignment of the liquid crystal in the liquid crystal layer 335 . The first insulating layer 320 may be a transparent insulating layer. For example, the first insulating layer 320 is an organic type, and may include polyimide, polyacrylate, epoxy, polyvinyl alcohol, parylene, polystyrene, polyacetate, polyvinylpyrrolidone, fluorine-based polymer, polyvinyl chloride, or these. It may include a compound including at least one repeating unit of As another example, the first insulating layer 320 is inorganic, silicon oxide (SiO), silicon nitride (SiN), silicon oxynitride (SiON), silicon carbide (SiC), silicon oxycarbide (SiOC), or these may include a combination of As another example, the first insulating layer 320 may include a combination of the organic type and the inorganic type.

Referring to FIG. 8B , a silicon oxide pattern 330 that is a three-dimensional structure may be formed on the first insulating layer 320 . The silicon oxide pattern 330 may be formed in a lattice shape to distinguish sub-pixels of the liquid crystal layer 335 , which will be described later. The silicon oxide pattern 330 may be formed by the method described above with reference to FIGS. 1A to 1C , and specifically to be formed using the electrohydrodynamic jet printing method described with reference to FIGS. 5, 6A, 6B and 7 above. can

For example, by electrohydrodynamic jet printing spraying a PDMS solution of high viscosity (eg, 1.0 cP to 1.0×10 ⁷ cP) on the first insulating layer 320, a lattice-shaped organic silicon pattern (not shown) ) can be formed. Since a high-viscosity PDMS solution is used, the organic silicon pattern may have a high aspect ratio. Next, the silicon oxide pattern 330 may be formed by irradiating ultraviolet rays in a wavelength range of 100 nm to 200 nm to the organic silicon pattern on the first insulating layer 320 .

Referring to FIG. 8C , a liquid crystal layer 335 filling empty spaces of the lattice of the silicon oxide pattern 330 may be formed. The liquid crystal layer 335 may include a liquid crystal as a host and a dichroic dye as a guest.

A second insulating layer 340 , a second electrode layer 350 , and an upper substrate 360 sequentially stacked may be formed on the liquid crystal layer 335 . A detailed description of the second insulating layer 340 , the second electrode layer 350 , and the upper substrate 360 is described above for the first insulating layer 320 , the first electrode layer 310 , and the It may be the same as described for the lower substrate 300 .

As an example of the present invention, a case in which the liquid crystal display according to the present invention is applied to a PM (passive matrix) driving type display device will be described. Although not shown, the plurality of first electrode layers 310 may be arranged side by side in a stripe shape. On the other hand, the plurality of second electrode layers 350 may be arranged in parallel with each other in the form of a stripe crossing the first electrode layers 310 .

As another example of the present invention, a case in which the liquid crystal display device according to the present invention is applied to an AM (active matrix) driving type display device will be described. Although not shown, the second electrode layer 350 may be integrally formed and used as a common electrode. In this case, the first electrode layer 310 may be connected to a thin film transistor (TFT) and patterned in a shape corresponding to the sub-pixels.

In the method of forming the semiconductor device according to the present embodiment, the silicon oxide pattern 330 can be easily formed using only the electrohydrodynamic jet printing method and ultraviolet irradiation without separate patterning, surface treatment, and/or heat treatment. have. Accordingly, damage to the first electrode layer 310 and the first insulating layer 120 can be minimized and the process can be simplified. Although this embodiment exemplifies a method of manufacturing a liquid crystal display device, a lattice structure of microfluid channels, or OLED, dye-sensitized solar cell, and electrochromic using the method of forming a three-dimensional structure according to the present embodiments A bank structure of an (electrochromic) device may be formed.

Claims (14)

providing an organosilicon precursor through a nozzle on the substrate to form an organosilicon pattern; and
Including forming a silicon oxide pattern by irradiating the organic silicon pattern with ultraviolet rays,
The organosilicon precursor contains polydimethylsiloxane (PDMS), and has a viscosity ^{of 1.0×10 2} cP to 1.0×10 ^{7 cP at 20° C. and 1 atm,}
Providing the organosilicon precursor on the substrate comprises:
generating an electric field between the substrate and the voltage difference between the nozzles; and
discharging the organosilicon precursor from the nozzle by the electric field,
The organosilicon precursor further comprises a solvent or ion capable of changing its viscosity and electrical conductivity,
The solvent is cyclopentanone, cyclohexanone, gamma-butyrolactone, toluene, methanol, ethanol, ethyl ether, N,N-dimethyl acetamide (N,N-dimethyl) acetamide), N-methyl-2-pyrrodinone, tetrahydrofuran, ethyl acetate and hexane, glycerol, triethylene glycol monomethyl It contains at least one selected from the group consisting of ether (Triethylene Glycol Monomethyl Ether), ethylene glycol (Ethylene glycol) and propylene glycol (Propylene glycol),
The ion includes an acid, a base or an ionic salt,
By adjusting the viscosity, the electrical conductivity, and the strength of the electric field of the organic silicon precursor, the size of the discharged organic silicon precursor drop is controlled,
The organic silicon pattern and the silicon oxide pattern have the same size,
The organic silicon pattern and the silicon oxide pattern, a method of forming a three-dimensional structure having a width of 30 μm to 50 μm and a height of 1 μm to 2 μm.
delete delete According to claim 1,
The ultraviolet light is a method of forming a three-dimensional structure having a wavelength range of 100 nm to 200 nm.
According to claim 1,
The irradiating of the ultraviolet rays is performed simultaneously with providing the organosilicon precursor on the substrate or after forming the organosilicon pattern.
delete According to claim 1,
The providing of the organic silicon precursor on the substrate includes further using a jet printing method or an imprint lithography method.
delete According to claim 1,
The organic silicon pattern and the silicon oxide pattern are each provided in plurality,
Forming the organic silicon patterns and the silicon oxide patterns includes:
forming a first silicon oxide pattern from the first organic silicon pattern; and
forming a second silicon oxide pattern from the second organic silicon pattern;
The method of forming a three-dimensional structure in which the second silicon oxide pattern is formed on the first silicon oxide pattern.
10. The method of claim 9,
The second organosilicon pattern is formed on the first organosilicon pattern,
The method of forming a three-dimensional structure in which the first and second silicon oxide patterns are formed together by irradiating ultraviolet rays to the stacked first and second organic silicon patterns.
According to claim 1,
Forming the organic silicon pattern includes forming the organic silicon pattern having a lattice shape on the substrate in a plan view,
The forming of the silicon oxide pattern may include forming the silicon oxide pattern in a lattice form by irradiating the organic silicon pattern with ultraviolet light.
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