This application is based on and claims priority under 35 U.S.C. § 119 to Korean Patent Application No. 10-2021-0133453, filed on Oct. 7, 2021, in the Korean Intellectual Property Office, the disclosure of which is incorporated by reference herein in its entirety.
The inventive concepts relate to integrated circuit (IC) devices, and more particularly, to methods of manufacturing an IC device using a plasma etching process.
Due to the development of the electronic technology, the downscaling of IC devices has rapidly progressed. Thus, structures of the IC devices have become complicated, and aspect ratios of structures included in the IC devices have greatly increased. Accordingly, processes of forming three-dimensional (3D) structures having high aspect ratios also have become stricter. In particular, when a plasma etching process is performed to form patterns having a relatively high aspect ratio during a process of manufacturing an IC device with a high integration, it is necessary to develop a technique of obtaining a desired vertical profile in a pattern obtained after the plasma etching process and a technique of ensuring a desired etch rate.
Some example embodiments of the inventive concepts provide methods of manufacturing an integrated circuit (IC) device, wherein when a plasma etching process is performed to form a pattern having a relatively high aspect ratio, a desired vertical profile and a desired etch rate may be ensured, thereby improving reliability and productivity of the IC device.
According to an aspect of the inventive concepts, a method of manufacturing an IC device includes forming an etching target structure on a substrate, forming an etching mask pattern having an opening on the etching target structure, etching a portion of the etching target structure through the opening to form a first hole in the etching target structure, forming a conductive polymer layer to cover the etching target structure inside the first hole, and etching another portion of the etching target structure through the first hole, in a state in which the etching target structure is covered by the conductive polymer layer inside the first hole, to form a second hole in the etching target structure. The second hole extends from the first hole toward the substrate.
According to another aspect of the inventive concepts, a method of manufacturing an IC device includes forming an insulating structure on a substrate, forming an etching mask pattern having an opening on the insulating structure, anisotropically etching the insulating structure through the opening to form a vertical hole, the vertical hole passing through the insulating structure. The anisotropically etching includes etching the portion of the insulating structure through the opening to form a preliminary hole in the insulating structure, forming a conductive polymer layer to cover the insulating structure inside the preliminary hole, and repeating, after the forming a conductive polymer layer, at least once cycle including sequentially performing the etching the portion of the insulating structure and the forming a conductive polymer layer.
According to another aspect of the inventive concepts, a method of manufacturing an IC device includes forming an insulating structure on a substrate, forming an etching mask pattern having an opening on the insulating structure, and anisotropically etching the insulating structure through the opening to form a vertical hole, the vertical hole passing through the insulating structure. The anisotropically etching includes etching a portion of the insulating structure through the opening in a first plasma atmosphere to form a first hole in the insulating structure, forming a conductive polymer layer by supplying a conductive polymer or precursors of the conductive polymer onto the substrate in a second plasma atmosphere, the conductive polymer layer covering sidewalls of the insulating structure inside the first hole, and etching another portion of the insulating structure through the first hole, in a state in which current flows through the conductive polymer layer in a third plasma atmosphere to form a second hole in the insulating structure. The second hole extends from the first hole toward the substrate in a vertical direction.
Some example embodiments of the inventive concepts will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings in which:
Hereinafter, some example embodiments will be described in detail with reference to the accompanying drawings. The same reference numerals are used to denote the same elements in the drawings, and repeated descriptions thereof will be omitted.
While the term “same,” “equal” or “identical” is used in description of example embodiments, it should be understood that some imprecisions may exist. Thus, when one element is referred to as being the same as another element, it should be understood that an element or a value is the same as another element within a desired manufacturing or operational tolerance range (e.g., ±10%).
When the terms “about” or “substantially” are used in this specification in connection with a numerical value, it is intended that the associated numerical value includes a manufacturing or operational tolerance (e.g., ±10%) around the stated numerical value. Moreover, when the words “about” and “substantially” are used in connection with geometric shapes, it is intended that precision of the geometric shape is not required but that latitude for the shape is within the scope of the disclosure. Further, regardless of whether numerical values or shapes are modified as “about” or “substantially,” it will be understood that these values and shapes should be construed as including a manufacturing or operational tolerance (e.g., ±10%) around the stated numerical values or shapes.
Referring to
As used herein, the term “substrate” may refer to a substrate itself, or a stack structure including a substrate and a certain layer, film, or the like on a surface of the substrate. In addition, the term “surface of a substrate” may refer to an exposed surface of a substrate itself, or an outer surface of a certain layer, film, or the like on the substrate. The substrate 10 may include a semiconductor substrate. In some example embodiments, the substrate 10 may include an element semiconductor, such as silicon (Si) or germanium (Ge). In other example embodiments, the substrate 10 may include a compound semiconductor, such as silicon germanium (SiGe), silicon carbide (SiC), gallium arsenide (GaAs), indium arsenide (InAs), or indium phosphide (InP). In still other example embodiments, the substrate 10 may have a silicon-on-insulator (SOI) structure. The substrate 10 may include a conductive region, for example, a doped well or a doped structure. In other example embodiments, the substrate 10 may include a transparent substrate.
The etching target structure 20 may include one selected from a semiconductor material, a conductive material, and an insulating material or a combination thereof.
In some example embodiments, the etching target structure 20 may include an insulating structure including at least one insulating film. The at least one insulating film may include a silicon oxide film, a silicon nitride film, a silicon oxynitride film, or a low-k dielectric film having a lower dielectric constant than the silicon oxide film. In some example embodiments, the etching target structure 20 may include tetraethylorthosilicate (TEOS), plasma-enhanced tetraethylorthosilicate (PE-TEOS), O3-TEOS, undoped silicate glass (USG), phosphosilicate glass (PSG), borosilicate glass (BSG), borophosphosilicate glass (BPSG), fluoride silicate glass (FSG), spin-on-glass (SOG), or a combination thereof.
In other example embodiments, the etching target structure 20 may include a semiconductor film. For example, the etching target structure 20 may include crystalline silicon, amorphous silicon, doped silicon, silicon germanium (SiGe), silicon carbide (SiC), or a combination thereof, without being limited thereto.
In still other example embodiments, the etching target structure 20 may include at least one conductive film. For example, the etching target structure 20 may include a doped polysilicon film, a metal silicide film, a metal film, a metal nitride film, or a combination thereof.
In process P2 of
In some example embodiments, the etching mask pattern MP may include a spin-on hardmask (SOH), an amorphous carbon layer (ACL), a polysilicon film, an oxide film, a nitride film, a photoresist film, or a combination thereof.
Referring to
The etching process for forming the first hole H11 in the etching target structure 20 according to process P3 of
In some example embodiments, the plasma etching apparatus may include a reactive ion etching (RIE) equipment, a magnetically enhanced RIE (MERIE) equipment, an inductively coupled plasma (ICP) equipment, a capacitively coupled plasma (CCP) equipment, a hollow-anode-type plasma equipment, a helical resonator plasma equipment, or an electron cyclotron resonance (ECR) plasma equipment
The reaction chamber of the plasma etching apparatus may include a first electrode and a second electrode, which may face each other in the vertical direction and each apply radio frequency (RF) power. The reaction chamber may provide a reaction space in which a plasma etching process is performed between the first electrode and the second electrode. The substrate 10 may be placed in the reaction space on the first electrode such that a main surface of the substrate 10 faces the second electrode. An etching process for forming the first hole H11 may be performed on the etching target structure 20 in a state in which the substrate 10 is placed on the first electrode.
To form the first hole H11 in the etching target structure 20 according to process P3 of
For example, when the etching target structure 20 includes a silicon oxide film, a silicon nitride film, or a combination thereof, the etching gas mixture may include a fluorinated hydrocarbon compound, a reactive gas, and a carrier gas. For example, the fluorinated hydrocarbon compound may include CF4, C2F6, C4F6, C4F8, CHF3, CH2F2, CH3F, C3H2F6, C4H2F6, C4F6, or a mixture thereof, without being limited thereto. The etching gas mixture may further include a fluorine-containing compound, for example NF3, HBr, and/or CH3F. The reactive gas may include O2, CO, CO2, NO, NO2, N2O, H2, NH3, HF, SO2, CS2, COS, CF3I, C2F3I, C2F5I, or a mixture thereof, without being limited thereto. The carrier gas may include argon (Ar), xenon (Xe), helium (He), neon (Ne), nitrogen (N2), krypton (Kr), or a mixture thereof, without being limited thereto.
In some example embodiments, the plasma etching process for forming the first hole H11 in the etching target structure 20 may be performed at room temperature (e.g., a temperature of about 20° C. to about 28° C.) to a relatively low process temperature of about 100° C., without being limited thereto.
In some example embodiments, while the plasma etching process for forming the first hole H11 in the etching target structure 20 is being performed according to process P3 of
When a portion of the etching target structure 20 is etched using plasma obtained from a fluorinated hydrocarbon compound including a carbon-fluorine (C—F) bond, radicals (e.g. CF, CF2, F, F2, and CHF) may be formed, and the etching target structure 20 may be etched in the vertical direction due to the radicals. In this case, charged particles (i.e., electrons and/or ions) supplied from plasma may be accumulated in the etching target structure 20 and the etching mask pattern MP during the etching process. In this case, when the etching process is continuously performed under the same conditions as before, an electric field around an etching target surface of the etching target structure 20 may be disturbed. Accordingly, inside the first hole H11, the radicals may enter a distorted path rather than a desired path in the vertical direction, and thus, a pattern having a profile with a desired shape may not be obtained. In addition, speed at which the radicals enter in the vertical direction inside the first hole H11 may be reduced, and thus, an etch rate of the etching target structure 20 may be non-uniform or reduced.
Referring to
As used herein, the term “a conductive polymer” may refer to a polymer that may exhibit conductivity due to intrinsic characteristics thereof without adding an additional conductive material.
The first conductive polymer layer CP1 may conformally cover respective exposed surfaces of the etching target structure 20 and the etching mask pattern MP. The first conductive polymer layer CP1 may include a portion, which extends from an entrance of the first hole H11 toward the substrate 10 in the vertical direction inside the first hole H11. When a subsequent plasma etching process is performed on the resultant structure of
The process of forming the first conductive polymer layer CP1 may be performed in a plasma atmosphere. In some example embodiments, the process of forming the first conductive polymer layer CP1 may be performed in the reaction chamber of the plasma etching apparatus, which has been described in process P2 above with reference to
In some example embodiments, to form the first conductive polymer layer CP1, precursors of a conductive polymer may be supplied onto the substrate 10 in the plasma atmosphere and plasma-polymerized to form the first conductive polymer layer CP1. As used herein, the term “precursor of a conductive polymer” refers to a compound that forms a conductive polymer due to polymerization.
In some example embodiments, the precursors of the conductive polymer may include a compound including a C5-C30 substituted or unsubstituted aromatic ring. For example, the precursors of the conductive polymer may be selected from thiophene, 3-alkyl thiophene, aniline, phenylvinyl sulfone, ortho-xylylene, meta-xylylene, para-xylylene, pyrrole, phenylene vinylene, phenylene, and derivatives thereof, without being limited thereto. The 3-alkyl thiophene may include 3-hexylthiophene or 3-octylthiophene, without being limited thereto.
In some example embodiments, while the process of forming the first conductive polymer layer CP1 is being performed in the reaction chamber of the plasma etching apparatus, which has been described in process P2 above with reference to
In other example embodiments, to form the first conductive polymer layer CP1, a conductive polymer including a C5-C30 substituted or unsubstituted aromatic ring may be supplied from the outside of the reaction chamber onto the substrate 10. In this case, a molecular weight Mw of the conductive polymer supplied from the outside of the reaction chamber onto the substrate 10 may be in a range of about 2,000 to about 200,000, for example, a range of about 10,000 to about 100,000, without being limited thereto. Thus, the first conductive polymer layer CP1 including the conductive polymer including the C5-C30 substituted or unsubstituted aromatic ring may be obtained.
In some example embodiments, the conductive polymer supplied onto the substrate 10 to form the first conductive polymer layer CP1 may be selected from polythiophene, poly(3-alkyl thiophene), poly(3,4-dialkylthiophene), poly(3,4-cycloalkylthiophene), poly(3,4-dialkoxythiophene), polyaniline, poly(phenyl vinyl sulfoxide), polypyrrole, polyparaphenylene, polyparaphenylenevinylene, poly-p-phenylene sulfide, polyfuran, polyselenophene, polytelurophene, poly(3,4-ethylenedioxythiophene), hydroxy methylated poly(3,4-ethylenedioxythiophene) (PEDOT), poly(3-hexylthiophene) (P3HT), poly(3,4-alkylenedioxy thiophene), N-methyl-2-pyrrolidone (NMP), and derivatives thereof, without being limited thereto. Polyaniline may be in the form of emeraldine salt (EB) having conductivity.
Referring to
During the etching of the other portion of the etching target structure 20 to form the second hole H12, the first conductive polymer layer CP1 covering a top surface of the etching mask pattern MP in the resultant structure of
Referring to
Referring to
During the etching of the still other portion of the etching target structure 20 to form the third hole H13, the second conductive polymer layer CP2 covering the top surface of the etching mask pattern MP in the resultant structure of
In some example embodiments, processes P3, P4, and P5 of
In some example embodiments, after the third hole H13, which is the vertical hole to be finally formed in the etching target structure 20, is formed as in the resultant structure shown in
Referring to
In some example embodiments, the processes described with reference to
As shown in
Referring to
The memory cell region MEC may be a region in which a memory cell array of an IC device is arranged, while the connection region CON may be a region in which structures configured to electrically connect the memory cell array in the memory cell region MEC to peripheral circuits. Connection regions CON may be on both sides of the memory cell region MEC in a first lateral direction (X direction), respectively. The substrate 110 may include a semiconductor material, such as polysilicon.
Referring to
A plurality of insulating layers 132 and a plurality of sacrificial insulating films 134 may be alternately stacked one by one on the upper conductive plate 118. The plurality of insulating films 132 may include silicon oxide film, and the plurality of sacrificial insulating films 134 may include silicon nitride. The plurality of sacrificial insulating films 134 may ensure spaces for forming a plurality of gate lines (refer to GL in
Referring to
In some example embodiments, the formation of the sacrificial pad unit 134S at the one end of each of the plurality of sacrificial insulating films 134 may include removing portions of the plurality of insulating films 132 to expose the one end of each of the plurality of sacrificial insulating films 134 included in the staircase structure ST, depositing an additional film on the exposed one end of each of the plurality of sacrificial insulating films 134, and patterning the additional film to leave the sacrificial pad unit 134S. The additional film may include the same material as a constituent material of the plurality of sacrificial insulating films 134.
Thereafter, an insulating block 133 may be formed to cover the staircase structure ST and the upper conductive plate 118 in the connection region CON. As a result, the obtained resultant structure may be planarized using a chemical mechanical polishing (CMP) process to remove undesired films, and thus, a top surface of the insulating film 132 that is at a highest level may be exposed.
Afterwards, in the memory cell region MEC and the connection region CON, a middle insulating film 136 may be formed to cover a top surface of each of the insulating film 132 and the insulating block 133 that is at the highest level. Each of the insulating block 133 and the middle insulating film 136 may include a silicon oxide film.
Referring to
To form the plurality of vertical holes including the plurality of channel holes CH, the plurality of word line cut holes WCH, and the plurality of dummy channel holes DCH, the same or substantially similar methods as the processes of forming the third hole H13, which have been described with reference to
Referring to
In some example embodiments, the plurality of channel structures 140 and the plurality of dummy channel structures 140D may be simultaneously formed. Each of the plurality of channel structures 140 and the plurality of dummy channel structure 140D may include a gate dielectric film 142, a channel region 144, a buried insulating film 146, and a drain region 148.
The gate dielectric film 142 may include a tunneling dielectric film, a charge storage film, and a blocking dielectric film, which are sequentially formed on the channel region 144. The tunneling dielectric film may include silicon oxide, hafnium oxide, aluminum oxide, zirconium oxide, and/or tantalum oxide. The charge storage film may include silicon nitride, boron nitride, silicon boron nitride, or doped polysilicon. The blocking dielectric film may include silicon oxide, silicon nitride, or a metal oxide having a higher dielectric constant than silicon oxide. The metal oxide may include hafnium oxide, aluminum oxide, zirconium oxide, tantalum oxide, or a combination thereof.
The channel region 144 may have a cylindrical shape. The channel region 144 may include doped polysilicon or undoped polysilicon.
The buried insulating film 146 may fill an inner space of the channel region 144. The buried insulating film 146 may include an insulating material. For example, the buried insulating film 146 may include silicon oxide, silicon nitride, silicon oxynitride, or a combination thereof. In some example embodiments, the buried insulating film 146 may be omitted. In this case, the channel region 144 in conjunction with the buried insulating film 146 may have a pillar structure having no empty inner space.
The drain region 148 may include doped polysilicon film. A plurality of drain regions 148 included in the plurality of channel structures 140 and the plurality of dummy channel structure 140D may be insulated from each other by the upper insulating film UL.
After the plurality of channel structures 140 and the plurality of dummy channel structure 140D are formed and before the plurality of word line cut structures WLC are formed, the insulating plate 112 may be selectively removed through the plurality of word line cut holes WCH only in the memory cell region MEC, from among the memory cell region MEC and the connection region CON, and the resultant empty space may be filled with a lower conductive plate 114. The lower conductive plate 114 may include a doped polysilicon film, a metal film, or a combination thereof. The metal film may include tungsten (W), without being limited thereto. In the memory cell region MEC, the lower conductive plate 114 and the upper conductive plate 118 may serve as a source region configured to supply current to vertical memory cells included in a cell array structure in the memory cell region MEC.
During the removal of the insulating plate in the memory cell region MEC, in the memory cell region MEC, portions of the gate dielectric film 142, which are included in the channel structure 140 and adjacent to the insulating plate 112, may be removed together with the insulating plate 112. Thus, the lower conductive plate 114 may pass through a partial region of the gate dielectric film 142 in a lateral direction and come into contact with the channel region 144.
In addition, after the lower conductive plate 114 is formed and before the plurality of word line cut structures WLC are formed, in the memory cell region MEC and the connection region CON, the plurality of sacrificial insulating films 134 and the sacrificial pad unit (refer to 134S in
Each of the plurality of gate lines GL and the plurality of conductive pad units GLA may include a metal (e.g., tungsten, nickel, cobalt, or tantalum), a metal silicide (e.g., tungsten silicide, nickel silicide, cobalt silicide, or tantalum silicide), doped polysilicon, or a combination thereof. Each of the plurality of word line cut structures WLC may include an insulating structure. In some example embodiments, the insulating structure may include silicon oxide, silicon nitride, silicon oxynitride, or a low-k dielectric material. For example, the insulating structure may include a silicon oxide film, a silicon nitride film, a silicon oxynitride (SiON) film, a silicon oxycarbonitride (SiOCN) film, a silicon carbonitride (SiCN) film, or a combination thereof.
In the IC device 100 manufactured using the method described with reference to
Referring to
The substrate 310 may include an element semiconductor (e.g., Si or Ge), or a compound semiconductor (e.g., SiGe, SiC, GaAs, InAs, or InP). The substrate 310 may include a conductive region, for example, a doped well or a doped structure. The plurality of active regions AC may be defined by a plurality of device isolation regions 312 formed in the substrate 310. The device isolation region 312 may include a silicon oxide film, a silicon nitride film, a silicon oxynitride film, or a combination thereof. The interlayer insulating film 320 may include a silicon oxide film. The plurality of conductive regions 324 may be connected to one terminal of a switching element (not shown) (e.g., a field-effect transistor (FET)) formed on the substrate 310. The plurality of conductive regions 324 may include polysilicon, a metal, a conductive metal nitride, a metal silicide, or a combination thereof.
Referring to
Referring to
The mold film 330 may include an oxide film. For example, the mold film 330 may include an oxide film (e.g., boro phospho silicate glass (BPSG), phospho silicate glass (PSG), and undoped silicate glass (USG). To form the mold film 330, a thermal chemical vapor deposition (CVD) process or a plasma-enhanced CVD (PECVD) process may be used. The mold film 330 may be formed to a thickness of about 1000 Å to about 20000 Å, without being limited thereto. In some example embodiments, the mold film 330 may include a support film (not shown). The support film may include a material having an etch selectivity with respect to the mold film 330. The support film may include a material having a relatively low etch rate with respect to the mold film 330 in an etching atmosphere (e.g., an etchant including ammonium fluoride (NH4F), hydrofluoric acid (HF), and water) that is used to remove the mold film 330 in a subsequent process. In some example embodiments, the support film may include silicon nitride, silicon carbonitride, tantalum oxide, titanium oxide, or a combination thereof.
Referring to
Referring to
To form the plurality of vertical holes including the plurality of holes SH, the same or substantially similar method as the processes of forming the third hole H13, which have been described with reference to
Referring to
The lower electrode-forming conductive film 350 may include a doped semiconductor, a conductive metal nitride, a metal, a metal silicide, a conductive oxide, or a combination thereof. In some example embodiments, the lower electrode-forming conductive film 350 may include a doped semiconductor, a conductive metal nitride, a metal, a metal silicide, conductive oxide, or a combination thereof. For example, the lower electrode-forming conductive film 350 may include niobium nitride (NbN), titanium nitride (TiN), titanium aluminum nitride (TiAlN), tantalum nitride (TaN), tantalum aluminum nitride (TaAlN), tungsten (W), tungsten nitride (WN), ruthenium (Ru), ruthenium oxide (RuO2), strontium ruthenium oxide (SrRuO3), iridium (Ir), iridium oxide (IrO2), platinum (Pt), platinum oxide (PtO), SrRuO3 (SRO), (Ba,Sr)RuO3 (BSRO), CaRuO3 (CRO), (La,Sr)CoO3) (LSCo), or a combination thereof, but a constituent material of the lower electrode-forming conductive film 350 according to the inventive concepts is not limited thereto. To form the lower electrode-forming conductive film 350, a CVD process, a metal organic CVD (MOCVD) process, or an atomic layer deposition (ALD) process may be used.
Referring to
To form the plurality of lower electrodes LE, a part of the upper portion of the lower electrode-forming conductive film 350 and the sacrificial pattern (refer to 342P in
Referring to
Referring to
In some example embodiments, the dielectric film 360 may include hafnium oxide, hafnium oxynitride, hafnium silicon oxide, zirconium oxide, zirconium silicon oxide, tantalum oxide, titanium oxide, barium strontium titanium oxide, barium titanium oxide, strontium titanium oxide, yttrium oxide, aluminum oxide, lead scandium tantalum oxide, lead zinc niobate, or a combination thereof, without being limited thereto. The dielectric film 360 may be formed using an ALD process. The dielectric film 360 may be formed to a thickness of about 50 Å to about 150 Å, without being limited thereto.
Referring to
The upper electrode UE may include a doped semiconductor, a conductive metal nitride, a metal, a metal silicide, conductive oxide, or a combination thereof. For example, the upper electrode UE may include NbN, TiN, TiAlN, TaN, TaAlN, W, WN, Ru, RuO2, SrRuO3, IrO2, Pt, PtO, SRO(SrRuO3), BSRO((Ba,Sr)RuO3), CRO(CaRuO3), LSCo((La,Sr)CoO3), or a combination thereof, without being limited thereto. To form the upper electrode UE, a CVD process, an MOCVD process, a physical vapor deposition (PVD) process, or an ALD process may be used.
In the method of manufacturing the IC device, which has been described with reference to
In the IC device 300 manufactured using the method described with reference to
While the inventive concepts have been particularly shown and described with reference to some example embodiments thereof, it will be understood that various changes in form and details may be made therein without departing from the spirit and scope of the following claims.
Number | Date | Country | Kind |
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10-2021-0133453 | Oct 2021 | KR | national |