CN115572540B - Composition for forming silicon dioxide layer, silicon dioxide layer and electronic device - Google Patents

Composition for forming silicon dioxide layer, silicon dioxide layer and electronic device Download PDF

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CN115572540B
CN115572540B CN202210699991.1A CN202210699991A CN115572540B CN 115572540 B CN115572540 B CN 115572540B CN 202210699991 A CN202210699991 A CN 202210699991A CN 115572540 B CN115572540 B CN 115572540B
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silicon dioxide
forming
dioxide layer
unsubstituted
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CN115572540A (en
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郭泽秀
金义贤
裵鎭希
司空峻
李忠宪
李汉松
任浣熙
张胜宇
赵炫洙
黄丙奎
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Samsung SDI Co Ltd
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    • H01L21/30604—Chemical etching

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Abstract

The present invention provides a composition for forming a silica layer, the composition comprising a silicon-containing polymer and a solvent, wherein a Refractive Index (RI) reduction ratio calculated from relation 1 is less than or equal to 3%; a silica layer made from the composition; an electronic device comprising a silicon dioxide layer. In relation 1, RI 100 : by coating the composition for forming a silicon dioxide layer on an 8 inch bare wafer to a thickness of 7200 angstroms and baking at 100 ℃ for 3 minutes, refractive index measured at 633 nm wavelength, and RI 250 : the refractive index measured at 633 nm wavelength was measured by coating the composition for forming the silica layer on an 8 inch bare wafer to a thickness of 7200 angstroms and baking at a temperature of 250 ℃ for 3 minutes. Refractive Index (RI) reduction rate (%) = { (RI) 100 ‑RI 250 )/RI 100 }*100。

Description

Composition for forming silicon dioxide layer, silicon dioxide layer and electronic device
Cross Reference to Related Applications
The present application claims priority and rights of korean patent application No. 10-2021-0080288 filed on the korean intellectual property office on month 21 of 2021, the entire contents of which are incorporated herein by reference.
Technical Field
The present disclosure relates to a composition for forming a silicon dioxide layer, and an electronic device fabricated from the silicon dioxide layer.
Background
In a flat panel display device, a thin film transistor (thin film transistor; TFT) including a gate electrode, a source electrode, a drain electrode, and a semiconductor is used as a switching element. The flat panel display device includes gate lines for transmitting a scan signal for controlling the thin film transistors and data lines for transmitting a signal applied to the pixel electrodes. In addition, an insulating layer for separating the same is formed between the semiconductor and the various electrodes. The insulating layer may be a silicon dioxide layer comprising a silicon component.
In order to provide a silicon oxide layer having insulating properties, a coating liquid containing inorganic polysilazane is used as Spin-On Dielectric (SOD). In this case, depending on the position of the substrate, the Thickness (THK) of the silicon oxide layer may deviate, which may have an adverse effect on the following process, and thus may have an adverse effect on the insulating properties of the product.
Specifically, when an inorganic polysilazane solution is coated and cured on a pattern wafer by a spin coating method, a phenomenon occurs in which the thickness of a silicon oxide layer varies depending on the position of the wafer, the position of a pattern block, and the like. When the layer has a non-uniform Thickness (THK), it may have an adverse effect on the following process, such as chemical mechanical polishing (chemicalmechanical polishing; CMP).
Accordingly, the conventional art has attempted to solve the problem by increasing the molecular weight of polysilazane synthesis, but it may cause the problem of gelation due to contact with moisture when increasing the molecular weight of polysilazane.
Disclosure of Invention
One embodiment provides a composition for forming a silicon dioxide layer that can form a film having a uniform thickness and less occurrence of void defects.
Another embodiment provides a silicon dioxide layer made from a composition for forming a silicon dioxide layer.
Another embodiment of the invention provides an electronic device comprising a silicon dioxide layer.
According to an embodiment, a composition for forming a silicon dioxide layer includes a silicon-containing polymer and a solvent, wherein a Refractive Index (RI) reduction ratio calculated by relation 1 is less than or equal to 3%.
[ relation 1]
Refractive Index (RI) reduction rate (%) = { (RI) 100 -RI 250 )/RI 100 }*100
In the formula (1) of the above-mentioned formula,
RI 100 : by coating the composition for forming a silicon dioxide layer on an 8-inch bare wafer to a thickness of 7200 angstroms and baking at 100 ℃ for 3 minutes, a refractive index measured at a wavelength of 633 nanometers, and
RI 250 : the refractive index measured at 633 nm wavelength was measured by coating the composition for forming the silica layer on an 8 inch bare wafer to a thickness of 7200 angstroms and baking at a temperature of 250 ℃ for 3 minutes.
The Refractive Index (RI) reduction may be less than 3%.
The silicon-containing polymer may be polysilazane, polysiloxazane, or a combination thereof.
The polysilazane may be an inorganic polysilazane.
The weight average molecular weight of the silicon-containing polymer may be from 4,000 g/mol to 20,000 g/mol.
The silicon-containing polymer may be included in an amount of 0.1 to 30 wt% based on the total amount of the composition for forming the silicon dioxide layer.
According to another embodiment, there is provided a silicon dioxide layer made from the aforementioned composition for forming a silicon dioxide layer.
According to another embodiment, an electronic device comprising the aforementioned silicon dioxide layer is provided.
By controlling the reactivity with moisture, a silicon dioxide layer with fewer void defects and uniform thickness can be achieved.
Drawings
Fig. 1 is a graph showing the correlation between RI reduction rate and standard deviation of silicon dioxide layer thickness of the compositions for forming a silicon dioxide layer according to examples 1 to 3 and comparative examples 1 to 4.
Fig. 2 shows FE-SEM images of the inside of a pattern wafer gap after wet etching of a silicon dioxide layer made of the composition for forming a silicon dioxide layer according to examples 1 to 3.
Fig. 3 shows FE-SEM images of the inside of the pattern wafer gap after wet etching of the silicon oxide layer manufactured from the compositions for forming a silicon oxide layer according to comparative examples 1 to 3.
Fig. 4 shows FE-SEM images of the inside of the pattern wafer gap after wet etching of the silicon oxide layer manufactured from the compositions for forming a silicon oxide layer according to comparative examples 4 and 5.
Fig. 5 is a schematic diagram showing the thickness measurement positions of a pattern wafer for thickness uniformity evaluation.
Detailed Description
Embodiments of the present invention will be described in detail so that those skilled in the art to which the present invention relates may easily practice the embodiments of the present invention. This disclosure may, however, be embodied in many different forms and should not be construed as limited to the example embodiments set forth herein.
In the drawings, the thickness of layers, films, panels, regions, etc. are exaggerated for clarity. Like reference numerals designate like elements throughout the specification. It will be understood that when an element such as a layer, film, region or substrate is referred to as being "on" another element, it can be directly on the other element or intervening elements may also be present. In contrast, when an element is referred to as being "directly on" another element, there are no intervening elements present.
In the present specification, when no definition is additionally provided, 'substituted' means that hydrogen of a compound is replaced by a substituent selected from the group consisting of: halogen atoms (F, br, cl or I), hydroxyl, alkoxy, nitro, cyano, amino, azido, amidino, hydrazino, hydrazono, carbonyl, carbamoyl, thiol, ester, carboxyl or salts thereof, sulfonic acid or salts thereof, phosphoric acid or salts thereof, C1 to C20 alkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, C6 to C30 aryl, C7 to C30 aralkyl, C1 to C30 alkoxy, C1 to C20 heteroalkyl, C2 to C20 heteroaryl, C3 to C20 heteroarylalkyl, C3 to C30 cycloalkyl, C3 to C15 cycloalkenyl, C6 to C15 cycloalkynyl, C2 to C30 heterocycloalkyl, and combinations thereof.
In addition, in the present specification, when a definition is not otherwise provided, 'hetero' means one including 1 to 3 hetero atoms selected from N, O, S and P.
In addition, in this specification,' means a moiety bonded to the same or different atoms or formulae.
Hereinafter, a composition for forming a silicon oxide layer according to an embodiment of the present invention is described.
The composition for forming a silicon dioxide layer according to the embodiment includes a silicon-containing polymer and a solvent, and a Refractive Index (RI) reduction ratio (reduction ratio) calculated from relation 1 is less than or equal to 3%.
[ relation 1]
Refractive Index (RI) reduction rate (%) = { (RI) 100 -RI 250 )/RI 100 }*100
In the formula (1) of the above-mentioned formula,
RI 100 : by coating the composition for forming a silicon dioxide layer on an 8-inch bare wafer to a thickness of 7200 angstroms and baking at 100 ℃ for 3 minutes, a refractive index measured at a wavelength of 633 nanometers, and
RI 250 : by coating the composition for forming the silicon dioxide layer on an 8 inch bare wafer to a thickness of 7200 angstroms, and baking at a temperature of 250 c for 3 minutes,refractive index measured at 633 nm wavelength.
The RI reduction rate indicates the extent to which the silicon-containing polymer reacts with moisture in the air.
In other words, the silicon-containing polymer reacts with moisture and thus forms si—o bonds, and the composition for forming a silica layer cures after coating, wherein the more si—o bonds, the lower the RI reduction rate. Therefore, since the RI reduction rate calculated according to relation 1 is small, the degree of formation of si—o bonds (i.e., reactivity with moisture) may be low.
The silica layer formed of the composition for a silica layer having a smaller RI reduction rate can suppress reactivity with moisture and volume expansion with moisture, and thus is uniformly formed.
In addition, since the formation of si—o bonds is suppressed, since gas generated when the silicon-containing polymer is formed into a silicon dioxide layer during curing can be easily removed, void defects caused on the surface of the silicon dioxide layer due to the gas can be greatly improved.
In other words, when relation 1 is greater than or equal to about 3, for example, less than about 3, the composition for forming a silicon oxide layer according to an embodiment may form a uniform film having smaller voids and exhibiting satisfactory gap filling.
In the present invention, M-2000 manufactured by j.a. Wu Lam company (j.a. wolam co.) is used to measure the refractive index at a wavelength of about 633 nm, and from this the refractive index reduction rate according to the baking temperature is calculated and used as an indicator of the reactivity with moisture.
The silicon-containing polymer used in the composition for forming the silicon dioxide layer may be, for example, an organic-inorganic polysilazane, an organic-inorganic polysiloxazane, or a combination thereof.
The silicon-containing polymer may include, for example, a moiety represented by chemical formula 1.
[ chemical formula 1]
In chemical formula 1，R 1 To R 3 Each independently is hydrogen, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C3 to C30 cycloalkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C7 to C30 aralkyl, substituted or unsubstituted C1 to C30 heteroalkyl, substituted or unsubstituted C2 to C30 heterocycloalkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C1 to C30 alkoxy, carboxyl, aldehyde, hydroxyl, or a combination thereof, and
"×" indicates a bond point.
For example, the silicon-containing polymer may be polysilazane produced from the reaction of a halosilane with ammonia.
For example, the polysilazane may be an inorganic polysilazane.
For example, the silicon-containing polymer included in the composition for forming a silicon dioxide layer may include a moiety represented by chemical formula 2.
[ chemical formula 2]
R of chemical formula 2 4 To R 7 Each independently is hydrogen, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C3 to C30 cycloalkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C7 to C30 aralkyl, substituted or unsubstituted C1 to C30 heteroalkyl, substituted or unsubstituted C2 to C30 heterocycloalkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C1 to C30 alkoxy, carboxyl, aldehyde, hydroxyl, or a combination thereof, and
"×" indicates a bond point.
For example, the silicon-containing polymer may include a moiety represented by chemical formula 1 and/or a moiety represented by chemical formula 2, and may further include a moiety represented by chemical formula 3.
[ chemical formula 3]
*-SiH 3
The moiety represented by chemical formula 3 is a structure terminated with hydrogen at the end, and may be contained in an amount of 15 to 35% by weight based on the total amount of si—h bonds of polysilazane or polysiloxazane structures. When the moiety of formula 3 is included in the polysilazane or polysiloxazane structure within the range, siH is prevented 3 Partially disperse into SiH 4 Simultaneously, the oxidation reaction is sufficiently performed during the heat treatment, and the occurrence of cracks in the filler pattern can be prevented.
The weight average molecular weight of the silicon-containing polymer may be, but is not limited to, 4,000 g/mol to 20,000 g/mol, for example 5,000 g/mol to 20,000 g/mol, for example 6,000 g/mol to 20,000 g/mol, for example 7,000 g/mol to 15,000 g/mol, for example 7,000 g/mol to 10,000 g/mol. When the weight average molecular weight of the silicon-containing polymer satisfies the above range, the silicon dioxide layer manufactured from the composition for forming a silicon dioxide layer may have excellent film thickness uniformity characteristics.
For example, the silicon-containing polymer may be included in an amount of 0.1 wt% to 30 wt% based on the composition used to form the silicon dioxide layer.
The solvent included in the composition for forming the silica layer is not particularly limited as long as it is a solvent capable of dissolving the silicon-containing polymer, and in particular, may include at least one selected from the group consisting of: benzene, toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene, triethylbenzene, cyclohexane, cyclohexene, decalin, dipentene, pentane, hexane, heptane, octane, nonane, decane, ethylcyclohexane, methylcyclohexane, cyclohexane, cyclohexene, p-menthane, dipropyl ether, dibutyl ether, anisole, butyl acetate, amyl acetate, methyl isobutyl ketone, and combinations thereof.
The composition for forming the silica layer may further comprise a thermal acid generator (thermal acidgenerator; TAG).
The thermal acid generator may be an additive to improve the developability of the composition for forming the silica layer and thereby allow the organosilane-based condensation polymer of the composition to develop at a relatively low temperature.
If the thermal acid generator generates acid (H) by heat + ) It may include any compound without particular limitation. In particular, the thermal acid generator may comprise a compound that is activated at 90 ℃ or above 90 ℃ and that generates sufficient acid and also has low volatility.
The thermal acid generator may be selected from the group consisting of nitrobenzyl tosylate, nitrobenzyl benzenesulfonate, phenol sulfonates, and combinations thereof, for example.
The thermal acid generator may be contained in an amount of 0.01 to 25 wt% based on the total amount of the composition for forming the silica layer, and within the range, the condensation polymer may be developed at a low temperature while having improved coating properties.
The composition for forming the silica layer may further comprise a surfactant.
The surfactant is not particularly limited, and may be, for example, a nonionic surfactant of: polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl alcohol, and the like; polyoxyethylene alkyl allyl ethers such as polyoxyethylene nonylphenol ether and the like; polyoxyethylene-polyoxypropylene block copolymers; polyoxyethylene sorbitol fatty acid esters such as sorbitol monolaurate, sorbitol monopalmitate, sorbitol monostearate, sorbitol monooleate, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol trioleate, polyoxyethylene sorbitol tristearate and the like; the fluorine-based surfactants of ifetro EF301 (EFTOP EF 301), ifetro EF303, ifetro EF352 (toshem Products co., ltd.)), migfield F171 (MEGAFACE F171), migfield F173 (japan Ink & chemistry company (daiippon Ink & chem., inc.)), flulura FC430 (FLUORAD FC 430), fluroller FC431 (Sumitomo 3M)), asahi AG710 (Asahi guard AG 710), salon S-382 (Surflon S-382), SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass co., ltd.)) and the like; other silicone surfactants such as organosiloxane polymer KP341 (Shin-Etsu Chemical co., ltd.)) and the like.
The surfactant may be contained in an amount of 0.001 to 10 wt% based on the total amount of the composition for forming the silica layer, and within the range, dispersion of the solution may be improved and at the same time, uniform thickness of the layer may be improved.
The composition for forming the silica layer may be in the form of a solution in which the silicon-containing polymer and components are dissolved in a mixed solvent.
According to another embodiment, a method of preparing a silicon dioxide layer may comprise: coating the aforementioned composition for forming a silica layer, drying the substrate coated with the aforementioned composition for forming a silica layer, and curing the composition for forming a silica layer.
For example, the composition for forming the silicon dioxide layer may be applied using a solution method such as spin coating, slot coating, inkjet printing.
The substrate may be, for example, a device substrate such as a semiconductor, a liquid crystal, or the like, but is not limited thereto.
When the coating of the composition for forming a silicon dioxide layer is completed, the substrate is then dried and cured. Drying and curing may be performed, for example, at a temperature greater than or equal to about 100 ℃ and may be performed by application of energy such as heat, ultraviolet light, microwaves, sound waves, or ultrasound.
For example, drying may be performed at about 100 ℃ to about 200 ℃, and the solvent in the composition for forming the silicon dioxide layer may be removed by drying. In addition, curing may be performed at about 250 ℃ to 1,000 ℃, and the composition for forming the silicon oxide layer may be converted into a thin oxide film by curing.
According to another embodiment of the present invention, there is provided a silicon dioxide layer manufactured according to the foregoing method. The silicon oxide layer may be, for example, an insulating layer, a separation layer, a hard coat layer, or the like, but is not limited thereto.
According to another embodiment of the present invention, an electronic device including a silicon dioxide layer is provided. The electronic device may be, for example, a display device, such as an LCD or LED; or a semiconductor device.
The following examples illustrate embodiments of the invention in more detail. However, these examples are illustrative, and the present disclosure is not limited thereto.
Preparation of composition for Forming silica layer
Synthesis example 1: preparation of an inorganic polysilazane semifinished product (A)
The inside of a2 liter reactor equipped with a stirrer and a temperature controller was replaced with dry nitrogen. Subsequently, 1,500 g of dry pyridine was put therein, and then cooled to 5 ℃. Then, 100 g of dichlorosilane was slowly added thereto over 1 hour. Subsequently, 70 g of ammonia was slowly added thereto over 3 hours. When ammonia was completely added thereto, dry nitrogen was added thereto for 30 minutes, and the ammonia remaining in the reactor was removed therefrom. The obtained white slurry product was filtered with a 1 μm TEFLON (tetrafluoroethylene) filter under a dry nitrogen atmosphere to obtain 1,000 g of filtrate. After 1,000 g of dried xylene was added thereto, the solids therein were adjusted to 60% by repeating the replacement of the solvent from pyridine to xylene with a rotary evaporator three times, and then filtered with a teflon (tetrafluoroethylene) filter having a pore size of 0.1 μm. By this method, an inorganic polysilazane semi-finished product (A) having a solid content of 60% and a weight average molecular weight of 3,000 g/mol was obtained.
(preparation of inorganic polysilazane)
Example 1
By combining 50 g of an inorganic polysilazane semifinished product (A) according to synthesis example 1, 400 g of dry pyridine, 80 g of dry xylene and 6500 cc of NH 3 The gas was placed in a 1 liter reactor equipped with a stirrer and a temperature controller, heated to 100 ℃, and the solvent was repeatedly replaced with dibutyl ether 4 times with a rotary evaporator at 70 ℃ to adjust the solid concentration to 20%, and then the solid was filtered with a 0.1 μm teflon (tetrafluoroethylene) filter to obtain a composition for forming a silica layer, which contains inorganic polysilazane, having a weight average molecular weight of 9,200 g/mol.
Example 2
By combining 50 g of the inorganic polysilazane semifinished product (A) according to synthesis example 1, 350 g of dry pyridine, 70 g of dryDry xylene and 3250 cc NH 3 The gas was placed in a 1 liter reactor equipped with a stirrer and a temperature controller, heated to 100 ℃, and the solvent was repeatedly replaced with dibutyl ether 4 times with a rotary evaporator at 70 ℃ to adjust the solid concentration to 20%, and then the solid was filtered with a 0.1 μm teflon (tetrafluoroethylene) filter to obtain a composition for forming a silica layer, which contains inorganic polysilazane, having a weight average molecular weight of 9,400 g/mol.
Example 3
50 g of the inorganic polysilazane semifinished product (A) according to synthesis example 1, 513 g of dry pyridine and 50 g of dry xylene were placed in a 1 liter reactor equipped with stirrer and temperature controller and heated to 100 ℃. During the reaction, the reactor pressure was maintained at 3 bar. When the reaction was completed, a composition for forming a silica layer having a weight average molecular weight of 7,100 g/mol and containing inorganic polysilazane was obtained by repeatedly replacing the solvent with dibutyl ether 4 times at 70 ℃ to adjust the solid concentration to 20% and filtering the solid with a 0.1 μm teflon (tetrafluoroethylene) filter.
Comparative example 1
50 g of the inorganic polysilazane semifinished product (A) according to synthesis example 1, 200 g of dry pyridine and 80 g of dry xylene were placed in a 1 liter reactor equipped with a stirrer and a temperature controller and heated to 100 ℃. During the reaction, the reactor pressure was maintained at 3 bar. When the reaction was completed, a composition for forming a silica layer having a weight average molecular weight of 10,500 g/mol and containing inorganic polysilazane was obtained by repeatedly replacing the solvent with dibutyl ether 4 times at 70 ℃ to adjust the solid concentration to 20% and filtering the solid with a 0.1 μm teflon (tetrafluoroethylene) filter.
Comparative example 2
A composition for forming a silica layer, which contains inorganic polysilazane and has a weight average molecular weight of 9,400 g/mol, was obtained by placing 50 g of the inorganic polysilazane semi-finished product (a) according to synthesis example 1, 150 g of dry pyridine, and 70 g of dry xylene into a 1 liter reactor equipped with a stirrer and a temperature controller, heating it to 100 ℃, and repeatedly replacing the solvent with dibutyl ether 4 times with a rotary evaporator at 70 ℃ to adjust the solid concentration to 20%, and filtering the solid with a 0.1 μm teflon (tetrafluoroethylene) filter.
Comparative example 3
A composition for forming a silica layer, which contains inorganic polysilazane and has a weight average molecular weight of 8,500 g/mol, was obtained by placing 50 g of the inorganic polysilazane semi-finished product (a) according to synthesis example 1, 120 g of dry pyridine, and 60 g of dry xylene into a 1 liter reactor equipped with a stirrer and a temperature controller, heating it to 100 ℃, and repeatedly replacing the solvent with dibutyl ether 4 times with a rotary evaporator at 70 ℃ to adjust the solid concentration to 20%, and filtering the solid with a 0.1 μm teflon (tetrafluoroethylene) filter.
Comparative example 4
A composition for forming a silica layer, which contains inorganic polysilazane and has a weight average molecular weight of 5,500 g/mol, was obtained by placing 50 g of the inorganic polysilazane semi-finished product (a) according to synthesis example 1, 513 g of dry pyridine, and 50 g of dry xylene into a 1 liter reactor equipped with a stirrer and a temperature controller, adding thereto 1.5 mol% of N, N' -tetramethyl-1, 6-hexamethylenediamine based on the weight of the inorganic polysilazane semi-finished product (a), heating the mixture to 100 ℃, repeatedly replacing the solvent with dibutyl ether 4 times with a rotary evaporator to adjust the solid concentration to 20%, and filtering the solid with a 0.1 μm teflon (tetrafluoroethylene) filter.
Comparative example 5
A composition for forming a silica layer, which contains inorganic polysilazane and has a weight average molecular weight of 9,500 g/mol, was obtained by placing 50 g of the inorganic polysilazane semi-finished product (a) according to synthesis example 1, 513 g of dry pyridine, and 50 g of dry xylene into a 1 liter reactor equipped with a stirrer and a temperature controller, adding thereto 3.0 mol% of N, N' -tetramethyl-1, 6-hexamethylenediamine based on the weight of the inorganic polysilazane semi-finished product (a), heating the mixture to 100 ℃, repeatedly replacing the solvent with dibutyl ether 4 times with a rotary evaporator to adjust the solid concentration to 20%, and filtering the solid with a 0.1 μm teflon (tetrafluoroethylene) filter.
Evaluation 1: measuring RI reduction rate
The compositions for forming a silicon dioxide layer according to examples 1 to 3 and comparative examples 1 to 5 were extracted for 3 cubic centimeters, respectively, then coated on the center of a bare wafer having a diameter of 8 inches, and spin-coated with a spin coater (MS-a 200, trioma co., ltd.) at 1500 rpm for 20 seconds, baked at 100 ℃ for 3 minutes, and measured for Refractive Index (RI) at 633 nm wavelength by using M-2000 (j.a. Wu Lam company) 100 )。
In addition, after baking at 250℃for 3 minutes, another Refractive Index (RI) at 633 nm wavelength was measured by using M-2000 (J.A. Wu Lam Co.) 250 )。
The refractive indexes at 100℃and 250℃are used to calculate the RI reduction rate according to the following relation 1.
[ relation 1]
Refractive Index (RI) reduction rate (%) = { (RI) 100 -RI 250 )/RI 100 }*100
In the formula (1) of the above-mentioned formula,
RI 100 : by coating the composition for forming a silicon dioxide layer on an 8-inch bare wafer to a thickness of 7200 angstroms and baking at 100 ℃ for 3 minutes, a refractive index measured at a wavelength of 633 nanometers, and
RI 250 : the refractive index measured at 633 nm wavelength was measured by coating the composition for forming the silica layer on an 8 inch bare wafer to a thickness of 7200 angstroms and baking at a temperature of 250 ℃ for 3 minutes.
The RI reduction rate calculated from relation 1 is shown in table 1.
Evaluation 2 evaluation of thickness uniformity
The compositions for forming a silicon oxide layer according to examples 1 to 3 and comparative examples 1 to 5 were coated on wafers having a diameter of 8 inches, which were patterned to have a line width of 0.2 to 10 micrometers and a space width of 0.2 micrometers, respectively, by using a spin coater (MS-a 200, fitted company).
Subsequently, the coated wafer was baked at 150℃for 3 minutes in oxygen (O) 2 ) Heating to 1,000deg.C under atmosphere, under H 2 /O 2 The silica layers formed from each of the compositions according to examples 1 to 5 and comparative examples 1 to 5 were obtained by curing for 1 hour under an atmosphere at the corresponding temperatures.
The patterned wafer coated with the silicon dioxide layer was cut into radial form along the diameter and then the thickness at the thickness monitor (TM, 90 microns x 90 microns) location was measured by using SEM (SU-8230, hitachi, ltd.).
Fig. 5 is a schematic diagram showing thickness measurement locations of a patterned wafer for thickness uniformity evaluation.
As shown in fig. 5, the TM locations include 17 radial dies, and the thickness of each die is measured at 5 points per 1 die, totaling 85 points.
After the initial coating, although the coating was performed in units of every 3 hours (0 hours, 3 hours, 6 hours, 9 hours) for 9 hours more, a change with time was observed. During the waiting time, virtual dispensing was performed at 5 minute intervals to prevent hardening of the nozzle, and the standard deviation of the thickness was calculated at 3 pieces per coating for a total of 12 pieces, and the results are shown in table 1.
Evaluation 3: evaluating void defects
Each composition for forming a silicon dioxide layer according to examples 1 to 3 and comparative examples 1 to 5 was extracted by 3 cubic centimeters and coated on an 8-inch wafer patterned to have a line width of 0.2 to 10 micrometers and a space width of 0.2 micrometers by using a spin coater (MS-a 200, fitted, inc.).
Subsequently, the coated wafer was heated and dried on a heating plate at 150 ℃ for 3 minutes, and moisture-cured at 1,000 ℃ for 60 minutes, to obtain a silica layer formed of each composition according to examples 1 to 3 and comparative examples 1 to 5.
Cutting cross-sections of samples to exposeExposing the fine pattern, immersing in 1 wt% dilute hydrofluoric acid (dilutehydrofluoric acid; DHF) for 120 seconds, washing with DI water, and washing with N 2 The gas was dried and then checked by FE-SEM photographs.
The criteria are given in the order of good/bad according to the void defect degree confirmed by the FE-SEM photograph, and are then shown in table 1.
( And (3) good: no gap exists in the gap, and the occupied area of the gap with the size smaller than 1.0 micron is smaller than or equal to 10 percent; the difference is: a void footprint of greater than or equal to 1.0 microns in size of less than 30%; bad: greater than or equal to 90% of the void footprint having a size of 1.0 microns or greater than 1.0 microns )
(Table 1)
Referring to table 1 and fig. 1 to 4, the compositions for a silicon dioxide layer according to examples 1 to 3 exhibit RI reduction rates of less than or equal to 3%, and specifically less than 3%, and thickness deviations of 10 microns or less than 10 microns, and improved void defects.
In contrast, the compositions for the silica layer according to comparative examples 1 to 5 exhibited RI reduction rates of more than 3% and thickness deviations of more than 10 μm.
Referring to fig. 2 to 4, the silicon oxide layer formed of the composition for a silicon oxide layer according to the example exhibited a relatively small number of voids in the cross section of each silicon oxide layer after wet etching, compared to the silicon oxide layer formed of the composition for a silicon oxide layer according to the comparative example.
While the invention has been described in connection with what is presently considered to be practical example embodiments, it is to be understood that the invention is not limited to the disclosed embodiments. On the contrary, it is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

Claims (5)

1. A composition for forming a silicon dioxide layer comprising:
inorganic polysilazane; and
at least one solvent selected from benzene, toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene, triethylbenzene, cyclohexane, cyclohexene, decalin, dipentene, pentane, hexane, heptane, octane, nonane, decane, ethylcyclohexane, methylcyclohexane, cyclohexane, cyclohexene, p-menthane, dipropyl ether, dibutyl ether, anisole, butyl acetate, amyl acetate, methyl isobutyl ketone, and combinations thereof,
wherein the inorganic polysilazane is contained in an amount of 0.1 to 30% by weight based on the total amount of the composition for forming the silica layer,
wherein the refractive index RI reduction ratio calculated by relation 1 is less than or equal to 3%:
[ relation 1]
Refractive index RI reduction% = { (RI) 100 -RI 250 )/RI 100 }*100
Wherein, in the relation 1,
RI 100 : by coating the composition for forming the silicon dioxide layer on an 8-inch bare wafer to a thickness of 7200 angstroms and baking at 100 ℃ for 3 minutes, refractive index measured at 633 nm wavelength, and
RI 250 : the silicon dioxide layer was formed by coating the composition for forming the silicon dioxide layer on an 8 inch bare wafer to a thickness of 7200 angstroms, and baking at a temperature of 250 c for 3 minutes, refractive index measured at 633 nm wavelength,
wherein the inorganic polysilazane includes a moiety represented by chemical formula 1 and a moiety represented by chemical formula 3,
[ chemical formula 1]
[ chemical formula 3]
*-SiH 3
In chemical formula 1, R 1 To R 3 Each independently is hydrogen, viaSubstituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C3 to C30 cycloalkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C7 to C30 aralkyl, substituted or unsubstituted C1 to C30 heteroalkyl, substituted or unsubstituted C2 to C30 heterocycloalkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C1 to C30 alkoxy, carboxyl, aldehyde, hydroxyl, or a combination thereof, and
the "x" indicates the bond point,
wherein the moiety represented by chemical formula 3 is contained in an amount of 15 to 35 wt% based on the total amount of Si-H bonds of the inorganic polysilazane.
2. The composition for forming a silica layer according to claim 1, wherein
The refractive index RI reduction is less than 3%.
3. The composition for forming a silica layer according to claim 1, wherein
The inorganic polysilazane has a weight average molecular weight of 4,000 g/mol to 20,000 g/mol.
4. A silicon dioxide layer manufactured from the composition for forming a silicon dioxide layer as claimed in any one of claims 1 to 3.
5. An electronic device comprising the silicon dioxide layer of claim 4.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030072895A1 (en) * 2001-08-28 2003-04-17 Osamu Sakakura Anti-reflection film, and silica layer
CN104114483A (en) * 2012-02-08 2014-10-22 Az电子材料（卢森堡）有限公司 Inorganic polysilazane resin
CN106662672A (en) * 2014-06-30 2017-05-10 三星电子株式会社 Silica film, optical member, and polarizing member
CN109957261A (en) * 2017-12-14 2019-07-02 三星Sdi株式会社 It is used to form composition, silicon dioxide layer and the electronic device of silicon dioxide layer
US20200369915A1 (en) * 2017-10-13 2020-11-26 Samsung Sdi Co., Ltd. Composition for forming silica layer, manufacturing method for silica layer, and silica layer

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030072895A1 (en) * 2001-08-28 2003-04-17 Osamu Sakakura Anti-reflection film, and silica layer
CN104114483A (en) * 2012-02-08 2014-10-22 Az电子材料（卢森堡）有限公司 Inorganic polysilazane resin
CN106662672A (en) * 2014-06-30 2017-05-10 三星电子株式会社 Silica film, optical member, and polarizing member
US20200369915A1 (en) * 2017-10-13 2020-11-26 Samsung Sdi Co., Ltd. Composition for forming silica layer, manufacturing method for silica layer, and silica layer
CN109957261A (en) * 2017-12-14 2019-07-02 三星Sdi株式会社 It is used to form composition, silicon dioxide layer and the electronic device of silicon dioxide layer

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