Patent Grant
10020185
This application claims priority to and the benefit of Korean Patent Application No. 10-2014-0135157, filed in the Korean Intellectual Property Office on Oct. 7, 2014, and Korean Patent Application No. 10-2014-0188905, filed in the Korean Intellectual Property Office on Dec. 24, 2014, the entire contents of all which are incorporated herein by reference.
1. Field
This disclosure relates to a composition for forming a silica layer, a silica layer, and an electronic device including the silica layer.
2. Description of the Related Art
With the development of semiconductor technology, researches on a semiconductor memory cell with high integration and a high speed have been made in order to increase integration in a smaller semiconductor chip and improve performance. However, as the semiconductor requires high integration and a space between wires becomes narrower, an RC delay, a cross-talk, deterioration of a response speed and/or the like may occur and thus, causes a problem in terms of a semiconductor interconnection. In order to solve this problem, appropriate separation among devices may be needed.
Accordingly, the appropriate separation among devices is performed by widely using a silica layer formed of a silicon-containing material as an interlayer insulating layer of a semiconductor device, a planarization layer, a passivation film, an insulation layer among devices and the like. The silica layer is used as a protective layer, an insulation layer and the like for a display device and the like as well as the semiconductor device. For example, Korean Patent Laid-Open No. 2002-0025680 discloses a semiconductor device including a silicon nitride layer, Korean Patent Laid-Open No. 2005-0104610 discloses a display device including an insulation layer as a silicon layer, and the entire contents of all which are incorporated herein by reference.
The silica layer is formed by in general coating a silicon-containing material in a set or predetermined region of a device and curing it, and thus, a material satisfying both gap-fill characteristics and gap etch characteristics is required when the silica layer is formed.
An aspect of an embodiment is directed toward a composition for forming a silica layer capable of ensuring gap-fill characteristics and gap etch characteristics (concurrently or simultaneously).
An aspect of another embodiment is directed toward a silica layer using the composition.
An aspect of yet another embodiment is directed toward an electronic device including the silica layer.
According to one embodiment, a composition for forming a silica layer includes a silicon-containing polymer having a weight average molecular weight of about 20,000 to about 70,000 and a polydispersity index of about 5.0 to about 17.0 and a solvent.
The silicon-containing polymer may include a silicon-containing polymer having a weight average molecular weight of about 20,000 to about 50,000 and a polydispersity index of about 5.0 to about 14.0, a silicon-containing polymer having a weight average molecular weight of greater than about 50,000 and less than or equal to about 70,000 and a polydispersity index of about 11.5 to about 17.0, or a combination thereof.
The silicon-containing polymer may be polysilazane, polysiloxazane, or a combination thereof.
The silicon-containing polymer may have a polydispersity index of about 5.3 to about 15.5.
The silicon-containing polymer may have a weight average molecular weight of about 22,000 to about 65,000.
The solvent may include at least one selected from benzene, toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene, triethylbenzene, cyclohexane, cyclohexene, decahydro naphthalene, dipentene, pentane, hexane, heptane, octane, nonane, decane, ethylcyclohexane, methylcyclohexane, cyclohexane, cyclohexene, p-menthane, dipropylether, dibutylether, anisole, butyl acetate, amyl acetate, methylisobutylketone, and a combination thereof.
The silicon-containing polymer may be included in an amount of about 0.1 to about 30 wt % based on the total amount of the composition for forming a silica layer.
The oxygen content of the silicon-containing polymer may range from about 0.01 wt % to about 3 wt % based on 100 wt % of the silicon-containing polymer, and the —SiH3 group content of the silicon-containing polymer may range from about 15% to about 40% based on the total amount of a Si—H bond in the silicon-containing polymer.
According to another embodiment, a silica layer is manufactured from (using) the composition.
According to yet another embodiment, an electronic device including the silica layer is provided.
In view of the foregoing and according to one or more embodiments, a silica layer capable of ensuring a film flatness and denseness inside gaps (concurrently or simultaneously) may be realized.
Exemplary embodiments of the present invention will hereinafter be described in more detail, and may be easily performed by those who have common knowledge in the related art. However, this disclosure may be embodied in many different forms and is not construed as limited to the exemplary embodiments set forth herein.
As used herein, when a definition is not otherwise provided, the term ‘substituted’ refers to one substituted with a substituent selected from a halogen atom (F, Br, Cl, or I), a hydroxy group, an alkoxy group, a nitro group, a cyano group, an amino group, an azido group, an amidino group, a hydrazino group, a hydrazono group, a carbonyl group, a carbamyl group, a thiol group, an ester group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, an alkyl group, a C2 to C16 alkenyl group, a C2 to C16 alkynyl group, aryl group, a C7 to C13 arylalkyl group, a C1 to C4 oxyalkyl group, a C1 to C20 heteroalkyl group, a C3 to C20 heteroarylalkyl group, a cycloalkyl group, a C3 to C15 cycloalkenyl group, a C6 to C15 cycloalkynyl group, a heterocycloalkyl group, and a combination thereof, instead of hydrogen of a compound.
Hereinafter, a composition for forming a silica layer according to one embodiment is described.
The composition for forming a silica layer according to one embodiment includes a silicon-containing polymer and a solvent.
The silicon-containing polymer may be a silicon (Si) atom-containing polymer without a particular limit, and may be, for example polysilazane, polysiloxazane, or a combination thereof.
The silicon-containing polymer may have a weight average molecular weight of about 20,000 to about 70,000, and a polydispersity index (PDI) of about 5.0 to about 17.0. According to one embodiment, the composition for forming a silica layer includes a silicon-containing polymer having a weight average molecular weight and a polydispersity index within each set or predetermined range and thus, may increase gap density of a layer as well as secure uniformity of the layer and thus, reducing or minimizing a defect inside the layer.
The silicon-containing polymer may include a silicon-containing polymer having a weight average molecular weight of about 20,000 to about 50,000 and a polydispersity index of about 5.0 to about 14.0, a silicon-containing polymer having a weight average molecular weight of greater than about 50,000 and less than or equal to about 70,000 and a polydispersity index of about 11.5 to about 17.0, or a combination thereof. The composition including the silicon-containing polymer satisfying a weight average molecular weight and a polydispersity index within each set or predetermined range has excellent etch characteristics as well as excellent coating properties and thus, form a uniform layer. In addition, the composition is cured for a relatively longer time and may stably form a layer.
Within the ranges, the silicon-containing polymer may have, for example a polydispersity index of about 5.3 to about 15.5, and the silicon-containing polymer may have, for example a weight average molecular weight of about 22,000 to about 65,000.
For example, the silicon-containing polymer may be included in an amount of about 0.1 to about 30 wt %, and specifically about 0.2 wt % to about 3 wt % based on the total amount of the composition for forming a silica layer.
When the silicon-containing polymer is included within the range, a composition including the silicon-containing polymer may be prevented or protected from contraction during heat treatment, and thus, a charge pattern formed thereof may be prevented or protected from cracking (forming a crack). More specifically, the silicon-containing polymer may be included in an amount of about 0.4 to about 2 wt %.
In addition, the silicon-containing polymer may include a moiety represented by —SiH3 at the terminal end, and the —SiH3 group content of the silicon-containing polymer may range from about 15% to about 40% based on the total amount of a Si—H bond in the silicon-containing polymer. Herein, the oxygen content is measured by using FlashEA 1112 (Thermo Fisher Scientific Inc.), and the SiH3/SiH is measured by using proton NM of 200 MHz: AC-200 (Bruker Co.).
The silicon-containing polymer may be included in an amount of about 0.1 to about 30 wt % based on the total amount of the composition for forming a silica layer. When the silicon-containing polymer is included within the range, appropriate viscosity may not only be maintained but an even and uniform layer may also be formed without a gap (a void) during gap-fill.
The solvent may use an aromatic compound, an aliphatic compound, a saturated hydrocarbon compound, ethers, esters, ketones, and/or the like, and may be specifically selected from benzene, toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene, triethylbenzene, cyclohexane, cyclohexene, decahydro naphthalene, dipentene, pentane, hexane, heptane, octane, nonane, decane, ethylcyclohexane, methylcyclohexane, cyclohexane, cyclohexene, p-menthane, dipropylether, dibutylether, anisole, butyl acetate, amyl acetate, methylisobutylketone, and a combination thereof.
In particular, at least one of the solvents has a high boiling point of greater than or equal to 130° C. Accordingly, flatness of a layer may be increased.
The solvent may be included in a balance amount except for the components based on the total weight of the composition for forming a silica layer.
The composition for forming a silica layer may further include a thermal acid generator (TAG).
The thermal acid generator may include any compound without particular limit, if it generates acid (H+) by heat. In particular, it may include a compound activated at 90° C. or higher and generating sufficient acid and also, having low volatility. Such a thermal acid generator may be, for example selected from nitrobenzyl tosylate, nitrobenzyl benzenesulfonate, phenol sulfonate, and a combination thereof.
The thermal acid generator may be included in an amount of about 0.01 to about 25 wt % based on the total amount of the composition for forming a silica layer.
The composition for forming a silica layer may further include a surfactant.
The surfactant is not particularly limited, and may be, for example: a non-ionic surfactant such as polyoxyethylene alkyl ethers (such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, or the like), polyoxyethylene alkylallyl ethers (such as polyoxyethylenenonyl phenol ether, or the like), polyoxyethylene⋅polyoxypropylene block copolymers, polyoxyethylene sorbitan fatty acid ester (such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monoleate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, or the like); a fluorine-based surfactant of EFTOP EF301, EF303, EF352 (Tochem Products Co., Ltd.), MEGAFACE F171, F173 (Dainippon Ink & Chem., Inc.), FLUORAD FC430, FC431 (Sumitomo 3M), Asahi guardAG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.), and/or the like; and/or other silicone-based surfactant (such as a organosiloxane polymer KP341 (Shin-Etsu Chemical Co., Ltd.), or the like).
The surfactant may be included in an amount of about 0.001 to about 10 wt % based on the total amount of the composition for forming a silica layer. Within the range, dispersion of a solution, uniformity in thickness, and filling properties of a layer may be improved.
According to another embodiment, a silica layer is manufactured from (using) the composition.
The method of manufacturing a silica layer (e.g., a silica-based insulation layer) includes coating the composition on a substrate; drying the substrate coated with the composition; and curing the substrate.
The composition for forming a silica layer may be in the form of a solution including the silicon-containing polymer and a solvent, and may be coated using a solution process, for example spin coating, slit coating, screen printing, inkjet, ODF (one drop filling) or a combination thereof. The curing process of the substrate may include heat-treating at a temperature, for example about 150° C. or greater.
The silica layer may be, for example an insulation layer, a filling layer, a protective layer (such as a hard coating or the like), a semiconductor capacitor, and/or the like. The insulation layer may be used, for example between a transistor device and a bitline, between a transistor device and a capacitor, without limitation.
According to another embodiment, an electronic device including the silica layer is provided. The electronic device may include a display device, a semiconductor, an image sensor, and/or the like.
Hereinafter, the following examples illustrate embodiments of the present invention in more detail. However, these examples are exemplary, and the present disclosure is not limited thereto.
Preparation of Composition for Forming Silica Layer
The internal atmosphere of a reactor equipped with a 2 L agitator and a temperature controller was substituted with dry nitrogen. 1,500 g of dry pyridine was put in the reactor, and then, the reactor was maintained at 0° C. Subsequently, 100 g of dichlorosilane was slowly injected thereinto over one hour. Next, 70 g of ammonia was slowly injected thereinto over 3 hours, while the reactor was agitated. Then, dry nitrogen was injected thereinto over 30 minutes, and ammonia remaining in the reactor was removed. The obtained white slurry-phased product was filtered through a 1 μm Teflon filter under a dry nitrogen atmosphere, thereby obtaining 1,000 g of a filtered solution. Then, 1,000 g of dry xylene was added thereto, the solvent of the mixture was repetitively substituted from pyridine to xylene, three times, by using a rotary evaporator to adjust its concentration into 30 wt %, and the concentrated product was filtered through a Teflon filter having a pore size of 0.03 μm.
300 g of dry pyridine was added to the filtered solution, and the mixture was heated at 100° C. until its weight average molecular weight reached 23,000.
Then, 1000 g of dry dibutylether was added thereto, and a solvent in the obtained mixture was repetitively substituted with dibutylether, three times, by using a rotary evaporator to adjust its solid (concentration) into 20 wt %.
Accordingly, polysilazane having a weight average molecular weight of 23,000 and a polydispersity index of 4.8 was obtained through the process. In the present specification, the weight average molecular weight and polydispersity index of the polysilazane were respectively measured by using GPC (PLC Pump 1515, RI Detector 2414) made by Waters.
Subsequently, the obtained polysilazane solution was filtered, thereby preparing a composition for forming a silica layer.
A heat treatment was performed through the same process as Comparative Example 1 until the weight average molecular weight became 100,000. Then, a composition for forming a silica layer was prepared by filtering the polysilazane dibutylether solution having a weight average molecular weight of 100,000 and a polydispersity index of 13.5 through the same solvent substitution manner as Comparative Example 1.
A heat treatment was performed through the same process as Comparative Example 1 until the weight average molecular weight became 140,000. Then, a composition for forming a silica layer was prepared by filtering the polysilazane dibutylether solution having a weight average molecular weight of 140,000 and a polydispersity index of 17.5 through the same solvent substitution manner as Comparative Example 1.
A heat treatment was performed through the same process as Comparative Example 1 until the weight average molecular weight became 8,000. Then, a polysilazane dibutylether solution having a weight average molecular weight of 8,000 and a polydispersity index of 2.9 was obtained through the same solvent substitution manner as Comparative Example 1.
The solution was mixed with the polysilazane dibutylether solution according to Comparative Example 2 in a weight ratio of 8:2, thereby obtaining a polysilazane dibutylether solution having a weight average molecular weight of 23,000 and a polydispersity index of 6.4. The obtained polysilazane solution was filtered, thereby preparing a composition for forming a silica layer.
A heat treatment was performed through the same process as Comparative Example 1 until a weight average molecular weight became 8,000. Then, a polysilazane dibutylether solution having a weight average molecular weight of 8,000 and a polydispersity index of 2.9 was obtained through the same solvent substitution manner as Comparative Example 1.
The solution was mixed with the polysilazane dibutylether solution of Comparative Example 3 in a weight ratio of 9:1, thereby obtaining a polysilazane dibutylether solution having a weight average molecular weight of 23,000 and a polydispersity index of 7.3. The obtained polysilazane solution was filtered, thereby preparing a composition for forming a silica layer.
A heat treatment was performed through the same process as Comparative Example 1 until a weight average molecular weight became 8,000. Then, a polysilazane dibutylether solution having a weight average molecular weight of 8,000 and a polydispersity index of 2.9 was obtained through the same solvent substitution manner as Comparative Example 1.
The solution was mixed with the polysilazane dibutylether solution of Comparative Example 2 in a weight ratio of 6:4, thereby obtaining a polysilazane dibutylether solution having a weight average molecular weight of 46,000 and a polydispersity index of 11.7. The obtained polysilazane solution was filtered, thereby preparing a composition for forming a silica layer.
A heat treatment was performed through the same process as Comparative Example 1 until a weight average molecular weight became 8,000. Then, a polysilazane dibutylether solution having a weight average molecular weight of 8,000 and a polydispersity index of 2.9 was obtained through the same solvent substitution manner as Comparative Example 1.
The solution was mixed with the polysilazane dibutylether solution of Comparative Example 3 in a weight ratio of 3:1, thereby obtaining a polysilazane dibutylether solution having a weight average molecular weight of 46,000 and a polydispersity index of 12.6. The obtained polysilazane solution was filtered, thereby preparing a composition for forming a silica layer.
A heat treatment was performed through the same process as Comparative Example 1 until a weight average molecular weight became 8,000. Then, a polysilazane dibutylether solution having a weight average molecular weight of 8,000 and a polydispersity index of 2.9 was obtained through the same solvent substitution manner as Comparative Example 1.
The solution was mixed with the polysilazane dibutylether solution of Comparative Example 2 in a weight ratio of 4:6, thereby obtaining a polysilazane dibutylether solution having a weight average molecular weight of 61,000 and a polydispersity index of 14.9. The obtained polysilazane solution was filtered, thereby preparing a composition for forming a silica layer.
A heat treatment was performed through the same process as Comparative Example 1 until a weight average molecular weight became 8,000. Then, a polysilazane dibutylether solution having a weight average molecular weight of 8,000 and a polydispersity index of 2.9 was obtained through the same solvent substitution manner as Comparative Example 1.
The solution was mixed with the polysilazane dibutylether solution of Comparative Example 3 in a weight ratio of 6:4, thereby obtaining a polysilazane dibutylether solution having a weight average molecular weight of 61,000 and a polydispersity index of 15.4. The obtained polysilazane solution was filtered, thereby preparing a composition for forming a silica layer.
A heat treatment was performed through the same process as Comparative Example 1 until a weight average molecular weight became 10,000. Then, a polysilazane dibutylether solution (1) having a weight average molecular weight of 10,000 and a polydispersity index of 3.2 was obtained through the same solvent substitution manner as Comparative Example 1.
Then, a heat treatment was performed through the same process as Comparative Example 1 until a weight average molecular weight became 30,000. Then, a polysilazane dibutylether solution (2) having a weight average molecular weight of 30,000 and a polydispersity index of 5.8 was obtained through the same solvent substitution manner as Comparative Example 1.
Then, the polysilazane dibutylether solutions (1) and (2) were mixed in a ratio of 4:6 (weight ratio), and then, a polysilazane dibutylether solution having a weight average molecular weight of 22,000 and a polydispersity index of 5.3 was obtained. The obtained polysilazane solution was filtered, thereby preparing a composition for forming a silica layer.
The specifications of the gel permeation chromatography (GPC) used are as below:
1. Model
2. Measurement Conditions
3. Calibration Curve
Each composition for forming a silica layer according to Comparative Examples 1 to 3 and Examples 1 to 7 was coated on a patterned silicon wafer and baked to form a thin film. A pattern of the patterned silicon wafer has a width of about 40 nm, and a depth of about 1 μm. Subsequently, after attaching the cross-section of the film to a mount, platinum sputtering was performed with 6 mA for 8 seconds by using an HR coater. The pre-treated samples were magnified 100,000 times by using an electron microscope (S5500, Hitachi Ltd.) and examined. Fifty trenches were randomly selected in the samples. Then, samples having a void in the fifty trenches were evaluated as “Unfavorable”, and samples having no void in the fifty trenches were evaluated as “Good”. The results are provided in the following Table 1.
Referring to Table 1,
Evaluation 2: Gap Etch Characteristics
Each composition for forming a silica layer according to Comparative Examples 1 to 3 and Examples 1 to 7 was coated on a patterned silicon wafer and then, baked, thereby forming a thin film. Subsequently, the cross-section of the film was dipped in an etching solution (an aqueous solution including HF of 0.5 wt %) for 30 seconds while the etching solution was maintained at 18° C. and then, cleaned with pure water for 30 seconds. Then, moisture remaining there was removed by using nitrogen. Then, the cross-section was attached to a mount and then, Pt-sputtered with 6 mA for 8 seconds by using an HR coater. The pre-treated sample was magnified 100,000 times by using an electron microscope (S5500, Hitachi Ltd.), and examined. The gap etch characteristics were evaluated according to a degree of a vacant space in the samples.
The results are provided in the following Table 2.
Referring to Table 2, and
Evaluation 3: Gelation Time
The compositions for forming a silica layer according to Comparative Examples 1 to 3 and Examples 1 to 7 were respectively filled in a half of a 40 ml glass vial and allowed to stand in a clean room at 22° C./50RH %. Then, the glass vial was examined with naked eyes every hour to check whether it was gelated or not. The gelation time means a required time for the composition to become a gel state. The gelation time of less than or equal to 7 hours was unfavorable, the gelation time ranging from greater than 7 hours to less than or equal to 12 hours was good, and the gelation time of greater than or equal to 12 hours was very good.
The results are provided in the following Table 3.
Referring to Table 3, the compositions for forming a silica layer according to Examples 1 to 7 showed a gelation time result of “good” or “very good”, while the compositions for forming a silica layer according to Comparative Examples 2 and 3 showed a gelation time result of “unfavorable”. These results are that a layer formed of a polysilazane composition having weight average molecular weight and a polydispersity index within each set or predetermined range according to example embodiments showed relatively long gelation time and thus, excellent stability of the composition.
Expressions such as “at least one of,” when preceding a list of elements, modify the entire list of elements and do not modify the individual elements of the list. Further, the use of “may” when describing embodiments of the inventive concept refers to “one or more embodiments of the inventive concept.” Also, the term “exemplary” is intended to refer to an example or illustration.
It will be understood that when an element or layer is referred to as being “on”, “connected to”, “coupled to”, or “adjacent to” another element or layer, it can be directly on, connected to, coupled to, or adjacent to the other element or layer, or one or more intervening elements or layers may be present. In contrast, when an element or layer is referred to as being “directly on,” “directly connected to”, “directly coupled to”, or “immediately adjacent to” another element or layer, there are no intervening elements or layers present.
As used herein, the term “substantially,” “about,” and similar terms are used as terms of approximation and not as terms of degree, and are intended to account for the inherent deviations in measured or calculated values that would be recognized by those of ordinary skill in the art.
Also, any numerical range recited herein is intended to include all subranges of the same numerical precision subsumed within the recited range. For example, a range of “1.0 to 10.0” is intended to include all subranges between (and including) the recited minimum value of 1.0 and the recited maximum value of 10.0, that is, having a minimum value equal to or greater than 1.0 and a maximum value equal to or less than 10.0, such as, for example, 2.4 to 7.6. Any maximum numerical limitation recited herein is intended to include all lower numerical limitations subsumed therein and any minimum numerical limitation recited in this specification is intended to include all higher numerical limitations subsumed therein. Accordingly, Applicant reserves the right to amend this specification, including the claims, to expressly recite any sub-range subsumed within the ranges expressly recited herein. All such ranges are intended to be inherently described in this specification such that amending to expressly recite any such subranges would comply with the requirements of 35 U.S.C. § 1 12, first paragraph, and 35 U.S.C. § 132(a).
As used herein, the terms “use,” “using,” and “used” may be considered synonymous with the terms “utilize,” “utilizing,” and “utilized,” respectively.
The electronic device may be implemented with logic gates or with any other embodiment of a processing unit or processor. The term, “processing unit” or “processor”, is used herein to include any combination of hardware, firmware, and software, employed to process data or digital signals. Processing unit hardware may include, for example, application specific integrated circuits (ASICs), general purpose or special purpose central processing units (CPUs), digital signal processors (DSPs), graphics processing units (GPUs), and programmable logic devices such as field programmable gate arrays (FPGAs). The electronic device and/or any other relevant devices or components according to embodiments of the present invention described herein may be implemented utilizing any suitable hardware or a combination of software, firmware, and hardware. For example, the various components of the device may be formed on or with one integrated circuit (IC) chip or on or with separate IC chips. Further, the various components of the device may be implemented on or with a flexible printed circuit film, a tape carrier package (TCP), a printed circuit board (PCB), or formed on or with one substrate.
While this invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims, and equivalents thereof.
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| Number | Date | Country | |
|---|---|---|---|
| 20160099145 A1 | Apr 2016 | US |
