US20010046777A1 - Method for forming a dielectric layer - Google Patents
Method for forming a dielectric layer Download PDFInfo
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- US20010046777A1 US20010046777A1 US09/364,053 US36405399A US2001046777A1 US 20010046777 A1 US20010046777 A1 US 20010046777A1 US 36405399 A US36405399 A US 36405399A US 2001046777 A1 US2001046777 A1 US 2001046777A1
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
- H01L21/02208—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
- H01L21/02211—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound being a silane, e.g. disilane, methylsilane or chlorosilane
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/314—Inorganic layers
- H01L21/316—Inorganic layers composed of oxides or glassy oxides or oxide based glass
- H01L21/31604—Deposition from a gas or vapour
- H01L21/31608—Deposition of SiO2
- H01L21/31612—Deposition of SiO2 on a silicon body
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
- H01L21/02164—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material being a silicon oxide, e.g. SiO2
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
- H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
- H01L21/02274—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition in the presence of a plasma [PECVD]
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31105—Etching inorganic layers
- H01L21/31111—Etching inorganic layers by chemical means
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/314—Inorganic layers
- H01L21/316—Inorganic layers composed of oxides or glassy oxides or oxide based glass
- H01L21/31604—Deposition from a gas or vapour
- H01L21/31625—Deposition of boron or phosphorus doped silicon oxide, e.g. BSG, PSG, BPSG
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/314—Inorganic layers
- H01L21/318—Inorganic layers composed of nitrides
- H01L21/3185—Inorganic layers composed of nitrides of siliconnitrides
Definitions
- the present invention relates generally to a method of fabricating a semiconductor device, and more particularly to a method of forming a dielectric layer in an integrated circuit.
- the dielectric layer is typically selected from a group consisting of USG (Undoped Silicate Glass), BPSG (BoroPhosphoSilicate Glass), and HDP (High Density Plasma) oxide.
- USG Undoped Silicate Glass
- BPSG BoPhosphoSilicate Glass
- HDP High Density Plasma oxide
- a BPSG layer can fill the recessed regions completely without void formation.
- a BPSG layer requires a high temperature (greater than about 800° C.) reflow process immediately after depositing the BPSG layer. Such a high temperature reflow undesirably causes diffusion of impurity ions around the junction, making it difficult to fabricate highly integrated devices with short channel lengths.
- a BPSG layer is etched quickly in a wet chemical (it has a relatively high etch rate with respect to a wet chemical) and thereby causes a poor vertical contact hole profile. As a result, it is difficult to form a contact hole with a small size. Also, due to a poor contact hole profile, a subsequently deposited conductive layer will have poor uniformity.
- An HDP oxide has advantages of both BPSG and USG.
- HDP advantageously fills recessed regions with a small thermal budget due to its low temperature process and with relatively good recessed region-filling characteristics.
- the aspect ratio is high, it is difficult to fill up a recessed region completely.
- an HDP oxide is not suitable for recessed regions having an aspect ratio of 3:1 or more.
- FIGS. 1 A- 1 C are cross-sectional views of a semiconductor device, taken at selected stages of a process of forming a dielectric layer according to the prior art.
- FIG. 1D is a perspective view of a portion of the semiconductor device.
- a device isolation layer 4 is formed to define an active region 2 and an inactive region (not designated) in and on a semiconductor substrate 1 .
- the device isolation layer 4 is made by a shallow trench isolation technique.
- a gate insulating layer 6 , gate electrode 8 , and gate etching mask 9 are sequentially formed on the active region 2 .
- the gate electrode 8 is formed by sequentially depositing a polysilicon layer and a silicide layer.
- the gate etching mask 9 is made of a silicon nitride layer to a thickness in the range of 1000 ⁇ to 2000 ⁇ . Then, impurity ions with low concentration are implanted into the active region 2 to form a low concentration source/drain region.
- Gate spacers 10 are formed on the side walls of both the gate electrode 8 and the gate etching mask 9 , thereby completely forming the gate structures.
- the gate spacers 10 are formed by an etching process such as an etch-back process after depositing a silicon nitride layer having a thickness in the range of 300 ⁇ to 1500 ⁇ .
- silicon oxide as a dielectric layer 16 is deposited over the substrate 1 .
- the top surface of the inter-layer dielectric 16 is planarized by a CMP (chemical mechanical polishing) process.
- CMP chemical mechanical polishing
- the foregoing method of forming a dielectric layer has the drawback of also forming voids 18 within the dielectric layer 16 as shown in FIG. 1B. Accordingly, when a polysilicon layer, for example, which is used to form pad electrodes is deposited over the semiconductor device, the polysilicon layer also penetrates into the voids 18 which are exposed by the CMP process, as shown in FIGS. 1 C- 1 D. As a result, a bridge between pad electrodes occurs. In addition, when a void occurs in a device isolation region, a bridge between gate electrodes can occur.
- the present invention was made in view of the above problems. Therefore, a feature of the present invention is directed toward providing a method of forming a void-free dielectric layer in a highly integrated device.
- a method of forming a void free dielectric layer on a semiconductor topology having recessed regions A first dielectric layer is deposited over the semiconductor topology. The first dielectric layer is etched to leave a part of the first dielectric layer at bottom portions of the recessed regions. A second dielectric layer is deposited over the semiconductor topology to fill up remainders of the recessed regions.
- a method of forming a dielectric layer in spaces between spaced apart gate lines with an insulating layer thereon, the gate lines having been formed on a semiconductor substrate A first inter-layer dielectric layer is deposited over the semiconductor substrate to fill the spaces. The first inter-layer dielectric layer is etched to leave a part of the first inter-layer dielectric on the spaces. A second inter-layer dielectric layer is deposited over the semiconductor substrate to fill up the remainders of the spaces.
- Each of the first and second inter-layer dielectric layers includes material having an etch selectivity with respect to the insulating layer.
- a method of forming a dielectric layer A trench is formed in a semiconductor substrate by etching. A first dielectric layer is deposited over the substrate including the trench. The first dielectric layer is etched to leave part of the first dielectric layer on a bottom of the trench. Finally, a second dielectric layer is deposited over the substrate to fill up the remainder of the trench.
- a method of forming a dielectric layer A first dielectric layer is deposited over a semiconductor substrate including a recessed region. The first dielectric layer is deposited by using helium gas as a sputtering gas. The first dielectric layer is dry etched to leave a part of the first dielectric layer on a bottom of the recessed region. A second dielectric layer is deposited over the semiconductor substrate to fill up a remainder of the recessed region with the second dielectric layer.
- FIGS. 1 A- 1 C are cross-sectional views of a semiconductor device, taken at selected stages of a process of forming a dielectric layer according to the prior art
- FIG. 1D is a perspective view of a portion of a semiconductor device, according to the prior art.
- FIGS. 2 A- 2 D are cross-sectional views of a semiconductor device, taken at selected stages of a process of forming a dielectric layer according to a first embodiment of the present invention.
- FIG. 3 is a cross-sectional view of a semiconductor device fabricated by a method of forming a dielectric layer according to a second embodiment of the present invention.
- a novel method of forming a dielectric layer according to the present invention provides a dielectric layer which is sufficiently free of voids to prevent bridges between conductive patterns.
- a first dielectric layer is deposited over an underlying region (i.e., a semiconductor substrate or one or more layers formed on the semiconductor substrate) including recessed regions formed therein.
- the first dielectric layer is then etched to leave a part of the first dielectric layer at the respective bottoms of the recessed regions.
- a second dielectric layer is then deposited over the underlying region including the first dielectric layer to fill up the recessed regions.
- FIGS. 2 A- 2 D show cross-sectional views of a semiconductor substrate at selected stages of a process of forming a dielectric layer.
- a device isolation layer 102 is formed to define an active region 101 and an inactive region (not designated) on a semiconductor substrate 100 .
- the device isolation layer 102 is formed by, for example, a LOCOS (LOCal Oxidation of Silicon) method or a trench isolation method. In this embodiment, the trench isolation method is used to form the device isolation layer 102 .
- gate structures 110 are formed on the gate insulating layer 104 .
- a recessed region is formed between each set of two adjacent gate structures.
- an upper width and a lower width of the recessed regions are 0.08 micrometers and 0.1 micrometers, respectively, and a height of the recessed regions is 0.4 micrometers.
- Formation of the gate structures 110 includes depositing a conductive layer for gate electrodes 106 on the gate insulating layer 104 .
- the conductive layer for the gate electrodes 106 is deposited to a thickness of about 2500 ⁇ .
- the conductive layer for the gate electrodes 106 is made of a multi-layer structure.
- a polysilicon layer 106 a having a thickness of about 1000 ⁇ , and a silicide layer 106 b having a thickness of about 1500 ⁇ , are formed, in this order, over the gate insulating layer 104 .
- a dielectric layer, also called a gate capping layer, which is used to create a gate capping mask 107 is deposited on the conductive layer for the gate electrodes 106 .
- the dielectric layer for the gate capping mask 107 has an etch selectivity with respect to subsequent inter-layer dielectrics 114 , 116 .
- the dielectric layer for the gate capping mask 107 can be silicon nitride, silicon oxide, silicon oxy-nitride, or any combination of these materials.
- the dielectric layer when it is deposited to a thickness in the range of about 1600 ⁇ to 3600 ⁇ (preferably about 2600 ⁇ ), it may be formed of a silicon nitride layer having a thickness of 1000 ⁇ to 2000 ⁇ (preferably about 1500 ⁇ ), a silicon oxide layer having a thickness of 200 ⁇ to 800 ⁇ (preferably about 500 ⁇ ), and a silicon oxynitride layer having a thickness of 400 ⁇ to 800 ⁇ (preferably about 600 ⁇ ).
- the silicon oxy-nitride layer serves as an anti-reflective layer.
- the dielectric layer for the gate capping mask 107 and the conductive layer for the gate electrodes 106 are sequentially etched using a gate forming mask to form the gate capping mask 107 and the gate electrodes 106 . Then impurity ions with low concentration are implanted into the active region 101 at both sides of the gate electrodes 106 to form source/drain regions of low concentration.
- the gate electrodes 106 may be formed by etching the dielectric layer for the gate capping mask 107 to form a patterned layer, and thereafter etching the conductive layer using the patterned layer as the gate forming mask.
- a dielectric layer for the gate spacers 108 may be deposited on the substrate 100 .
- the dielectric layer for the gate spacers 108 may be made of silicon nitride, silicon oxide, silicon oxy-nitride, or a combination of these materials, such as in the gate capping mask 107 , and is preferably made to a thickness in the range of about 300 ⁇ to 1500 ⁇ .
- the dielectric layer for the gate spacers 108 is preferably etched by an etch-back process to form gate spacers 108 on the side walls of a laminated layer which includes the gate electrode 106 and the gate capping mask 107 .
- an etch stopping layer 112 may be deposited over the resulting semiconductor structure (see also reference numeral 14 of FIG. 1A).
- the etch stopping layer 112 is preferably made of silicon nitride deposited to a thickness in the range of 50 ⁇ to 200 ⁇ .
- the etch stopping layer 112 is used to prevent the device isolation layer 102 and the active region 101 from being etched during the step of etching the later formed dielectric between gate electrodes down to the top surface of the substrate to form an opening.
- a first inter-layer dielectric 114 is deposited over the etch stopping layer 112 such that it almost fills a recessed region between adjacent gate structures 110 .
- the first inter-layer dielectric 114 is preferably made of a silicon oxide such as BPSG, USG, PE-TEOS, HDP oxide, or a combination thereof.
- the first inter-layer dielectric 114 is deposited to a thickness in the range of 300 ⁇ to 3000 ⁇ , preferably 2000 ⁇ . If HDP oxide formed by a CVD method is used, an inert gas such as argon (Ar) or helium (He) may be used as a sputtering gas.
- the first inter-layer dielectric 114 When the first inter-layer dielectric 114 is formed using He gas as a sputtering gas, it can be deposited under the following conditions: a low frequency power (400 kHz) in the range of 2000 W to 4000 W, a high frequency power (13.56 MHz) in the range of 500 W to 3000 W, and using a process gas including silane (SiH 4 ) gas with a flow rate in the range of 40 sccm to 120 sccm and O 2 gas with a flow rate in the range of 40 sccm to 300 sccm.
- the low frequency power is 3000 W
- the high frequency power is 1300 W
- the SiH 4 gas has a flow rate of 80 sccm
- the O 2 gas has a flow rate of 120 sccm.
- the first inter-layer dielectric 114 may have an improved deposition profile, as shown by reference numeral 115 in FIG. 2A. This is because re-sputtering of the first inter-layer dielectric 114 is low due to the fact that helium has an atomic mass of 4.
- the inter-layer dielectric 114 is etched to leave part of the inter-layer dielectric 114 on the bottoms of the recessed regions between the gate structures 110 , as shown in FIG. 2C.
- the etching process can be a wet etch. Wet etch is advantageously used because the space between adjacent recessed regions can be expanded further not only in a vertical direction, but also in a horizontal direction.
- the wet etch process may be performed by using a typical oxide etchant such as 200:1 HF, LAL (mixture of NH 4 F and HF), or BOE (buffered oxide etchant).
- a dry etch process can be performed, or wet and dry etch processes can be performed by in-situ.
- the dry etch process is preferably performed by using an etch gas based on at least one material selected from the group consisting of Ar, CF 4 , CHF 3 , He, CH 2 F 2 , and O 2 . It should also be clear that the etching may be performed by using two separate wet etch processes. Alternatively, a combination of dry and wet etch processes can be employed.
- FIGS. 2B and 2C schematically show in detail the process of etching the first inter-layer dielectric 114 using a combination of dry and wet etch processes, more particularly by first dry etching and then wet etching.
- the depth of the etching of the first inter-layer dielectric 114 is in the range of 150 ⁇ to 500 ⁇ , preferably 300 ⁇ .
- the dry etching process can be performed with the following conditions. Both the low frequency power (400 kHz) and the high frequency power (13.56 MHz) preferably have a range of 2000 W to 4500 W.
- the etch gas may be helium gas, O 2 gas, or a mixture thereof. Preferably, a mixture gas is used. When helium gas is used, it preferably has a flow rate of 390 sccm. When O 2 gas is used, it preferably has a flow rate of 30 sccm.
- the wet etch process which is performed immediately after the dry etch process can be performed with the following conditions.
- the first inter-layer dielectric 114 is etched in the range of 100 ⁇ to 400 ⁇ , preferably 200 ⁇ , in depth.
- the wet etch process is then performed by using a typical oxide etchant such as 200:1 HF, LAL, or BOE.
- a typical oxide etchant such as 200:1 HF, LAL, or BOE.
- a second inter-layer dielectric 116 is deposited over the substrate 100 , including the first inter-layer dielectric 114 , to fill up the recessed regions.
- a void free inter-layer dielectric 118 a combination of the first and second inter-layer dielectrics 114 and 116 , is formed as shown in FIG. 2D.
- the second inter-layer dielectric 116 can be made of the same material as that of the first inter-layer dielectric 114 , such as an HDP oxide.
- the second inter-layer dielectric 116 can be made of a material different from that of the first inter-layer dielectric 114 , such as USG or PE-TEOS.
- the second inter-layer dielectric 116 is deposited to a thickness in the range of 300 ⁇ to 3000 ⁇ , preferably 2800 ⁇ . Deposition of the second inter-layer dielectric 116 can be performed under the following conditions.
- the low frequency power has a range of 2000 W to 4000 W and the high frequency power has a range of 500 W to 4000 W.
- silane (SiH 4 ) gas has a flow rate in the range of 40 sccm to 120 sccm and O 2 gas has a flow rate in the range of 40 sccm to 300 sccm.
- helium gas is used as a sputtering gas.
- the low frequency power is 3000 W
- the high frequency power is 2000 W
- the flow rate of silane is 120 sccm
- the flow rate of helium is 390 sccm.
- the aspect ratio of the recessed regions can be reduced because part of the first inter-layer dielectric 114 is left behind in the recessed regions. Therefore, a void is not produced during the deposition of the second inter-layer dielectric 116 .
- the top surface of the second inter-layer dielectric 116 is planarized by using an etch-back process or a CMP process.
- FIG. 3 is a cross-sectional view of a semiconductor substrate depicting a method of forming a dielectric layer in accordance with a second embodiment of the present invention.
- a pad oxide 202 , a pad nitride 204 a, and an HTO oxide 204 b are deposited sequentially on a semiconductor substrate 200 and then patterned by using a photolithography process which is well-known in this art.
- a trench etch mask 204 is formed which comprises the pad nitride 204 a and the HTO oxide 204 b.
- the substrate 200 is etched using the trench etch mask 204 to form a trench 206 therein. Thermal oxidation is then performed to form an oxide film on both sidewalls and the bottom of the trench 206 .
- a first trench isolation layer 208 is deposited over the substrate 200 including the trench 206 .
- the first trench isolation layer 208 is preferably made of USG or HDP oxide.
- the first trench isolation layer 208 is etched so as to leave part of it on the bottom of the trench 206 .
- a void can be removed that may be formed during and after depositing the first trench isolation layer 208 .
- the etching of the first trench isolation layer 208 is performed by a dry etch process, a wet etch process, or a combination of dry and wet etch processes.
- a second trench isolation layer 210 is deposited to fill up the trench 206 .
- the second trench isolation layer 210 can be made of the same material as that of the first trench isolation layer 208 .
- the second trench isolation layer 210 can be made of a material different from that of the first trench isolation layer 208 , such as PE-TEOS.
- PE-TEOS a material different from that of the first trench isolation layer 208
- the processes of depositing the first and the second trench isolation layers 208 , 210 are preferably performed by using a sputtering gas such as argon gas or helium gas.
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Abstract
A dielectric layer is formed by depositing a first dielectric layer above a semiconductor substrate including recessed regions, etching the first dielectric layer to remove any voids and to lower the aspect ratio of the recessed regions, and depositing a second dielectric layer on the first dielectric layer in the recessed regions. The method is particularly useful when the aspect ratios are high for recessed regions formed between patterns.
Description
- 1. Field of the Invention
- The present invention relates generally to a method of fabricating a semiconductor device, and more particularly to a method of forming a dielectric layer in an integrated circuit.
- 2. Description of the Related Art
- As the integration density of semiconductor devices has been increasing, the pattern size of semiconductor devices has been decreasing. As an example, it is clear that design rules of less than 0.18 micrometers will be used for Giga DRAMs. When the minimum design rule of a memory cell array is scaled down, the aspect ratios of the structures within the cell array are increased. Such scaling-down may also increase the aspect ratio of recessed regions between the structures. The small size of the recessed regions causes them to be insufficiently filled by a filling material, such as a dielectric, which is deposited on them. As a result, a void is created as described inSilicon Processing for the VLSI Era, Vol. II, pp. 194-199 and U.S. Pat. No. 5,494,854. The void can cause a bridge between subsequently created conductive patterns.
- The dielectric layer is typically selected from a group consisting of USG (Undoped Silicate Glass), BPSG (BoroPhosphoSilicate Glass), and HDP (High Density Plasma) oxide. The use of each of these materials has its limitations. A BPSG layer can fill the recessed regions completely without void formation. However, a BPSG layer requires a high temperature (greater than about 800° C.) reflow process immediately after depositing the BPSG layer. Such a high temperature reflow undesirably causes diffusion of impurity ions around the junction, making it difficult to fabricate highly integrated devices with short channel lengths. In addition, a BPSG layer is etched quickly in a wet chemical (it has a relatively high etch rate with respect to a wet chemical) and thereby causes a poor vertical contact hole profile. As a result, it is difficult to form a contact hole with a small size. Also, due to a poor contact hole profile, a subsequently deposited conductive layer will have poor uniformity.
- Although not requiring the above-mentioned high temperature reflow process, a USG layer formed by chemical vapor deposition (CVD) does not completely fill the recessed regions. Such incomplete filling causes voids, and is not compatible with highly integrated devices.
- An HDP oxide has advantages of both BPSG and USG. HDP advantageously fills recessed regions with a small thermal budget due to its low temperature process and with relatively good recessed region-filling characteristics. However, when the aspect ratio is high, it is difficult to fill up a recessed region completely. In particular, an HDP oxide is not suitable for recessed regions having an aspect ratio of 3:1 or more.
- FIGS.1A-1C are cross-sectional views of a semiconductor device, taken at selected stages of a process of forming a dielectric layer according to the prior art. FIG. 1D is a perspective view of a portion of the semiconductor device.
- Referring to FIG. 1A, a
device isolation layer 4 is formed to define anactive region 2 and an inactive region (not designated) in and on asemiconductor substrate 1. Thedevice isolation layer 4 is made by a shallow trench isolation technique. Agate insulating layer 6,gate electrode 8, andgate etching mask 9 are sequentially formed on theactive region 2. Thegate electrode 8 is formed by sequentially depositing a polysilicon layer and a silicide layer. Thegate etching mask 9 is made of a silicon nitride layer to a thickness in the range of 1000 Å to 2000 Å. Then, impurity ions with low concentration are implanted into theactive region 2 to form a low concentration source/drain region. -
Gate spacers 10 are formed on the side walls of both thegate electrode 8 and thegate etching mask 9, thereby completely forming the gate structures. Thegate spacers 10 are formed by an etching process such as an etch-back process after depositing a silicon nitride layer having a thickness in the range of 300 Å to 1500 Å. - As shown in FIG. 1B, silicon oxide as a
dielectric layer 16 is deposited over thesubstrate 1. - Finally, as shown in FIGS.1C-1D, the top surface of the inter-layer dielectric 16 is planarized by a CMP (chemical mechanical polishing) process.
- However, the foregoing method of forming a dielectric layer has the drawback of also forming
voids 18 within thedielectric layer 16 as shown in FIG. 1B. Accordingly, when a polysilicon layer, for example, which is used to form pad electrodes is deposited over the semiconductor device, the polysilicon layer also penetrates into thevoids 18 which are exposed by the CMP process, as shown in FIGS. 1C-1D. As a result, a bridge between pad electrodes occurs. In addition, when a void occurs in a device isolation region, a bridge between gate electrodes can occur. - Therefore, there is a need for a process of depositing a void-free dielectric layer or removing a void already formed in a dielectric layer.
- The present invention was made in view of the above problems. Therefore, a feature of the present invention is directed toward providing a method of forming a void-free dielectric layer in a highly integrated device.
- In accordance with one aspect of the present invention, there is provided a method of forming a void free dielectric layer on a semiconductor topology having recessed regions. A first dielectric layer is deposited over the semiconductor topology. The first dielectric layer is etched to leave a part of the first dielectric layer at bottom portions of the recessed regions. A second dielectric layer is deposited over the semiconductor topology to fill up remainders of the recessed regions.
- In accordance with another aspect of the present invention, there is provided a method of forming a dielectric layer in spaces between spaced apart gate lines with an insulating layer thereon, the gate lines having been formed on a semiconductor substrate. A first inter-layer dielectric layer is deposited over the semiconductor substrate to fill the spaces. The first inter-layer dielectric layer is etched to leave a part of the first inter-layer dielectric on the spaces. A second inter-layer dielectric layer is deposited over the semiconductor substrate to fill up the remainders of the spaces. Each of the first and second inter-layer dielectric layers includes material having an etch selectivity with respect to the insulating layer.
- In accordance with another aspect of the present invention, there is provided a method of forming a dielectric layer. A trench is formed in a semiconductor substrate by etching. A first dielectric layer is deposited over the substrate including the trench. The first dielectric layer is etched to leave part of the first dielectric layer on a bottom of the trench. Finally, a second dielectric layer is deposited over the substrate to fill up the remainder of the trench.
- In accordance with another aspect of the present invention, there is provided a method of forming a dielectric layer. A first dielectric layer is deposited over a semiconductor substrate including a recessed region. The first dielectric layer is deposited by using helium gas as a sputtering gas. The first dielectric layer is dry etched to leave a part of the first dielectric layer on a bottom of the recessed region. A second dielectric layer is deposited over the semiconductor substrate to fill up a remainder of the recessed region with the second dielectric layer.
- The above features and advantages of the invention will become more apparent upon reference to the following description of specific embodiments and the attached drawings, wherein:
- FIGS.1A-1C are cross-sectional views of a semiconductor device, taken at selected stages of a process of forming a dielectric layer according to the prior art;
- FIG. 1D is a perspective view of a portion of a semiconductor device, according to the prior art;
- FIGS.2A-2D are cross-sectional views of a semiconductor device, taken at selected stages of a process of forming a dielectric layer according to a first embodiment of the present invention; and
- FIG. 3 is a cross-sectional view of a semiconductor device fabricated by a method of forming a dielectric layer according to a second embodiment of the present invention.
- Korean Application Nos. 98-31287, filed on Jul. 31, 1998, and 99-15624, filed on Apr. 30, 1999, are hereby incorporated by reference as if fully set forth herein.
- The preferred embodiment of the present invention will now be described with reference to the accompanying drawings. Referring to FIGS. 2 and 3, a novel method of forming a dielectric layer according to the present invention provides a dielectric layer which is sufficiently free of voids to prevent bridges between conductive patterns. According to the method, a first dielectric layer is deposited over an underlying region (i.e., a semiconductor substrate or one or more layers formed on the semiconductor substrate) including recessed regions formed therein. The first dielectric layer is then etched to leave a part of the first dielectric layer at the respective bottoms of the recessed regions. A second dielectric layer is then deposited over the underlying region including the first dielectric layer to fill up the recessed regions.
- When a certain layer is described to be “on” or “above” another layer or substrate, the certain layer may be directly on the other layer or substrate, and one or more additional layers may be interposed between the certain layer and the other layer or substrate. An analogous definition is intended for the words “below” and “under.”
- First Embodiment
- A first embodiment of the present invention will be described with reference to the accompanying drawings in FIGS.2A-2D which show cross-sectional views of a semiconductor substrate at selected stages of a process of forming a dielectric layer. Referring to FIG. 2A, a
device isolation layer 102 is formed to define anactive region 101 and an inactive region (not designated) on asemiconductor substrate 100. Thedevice isolation layer 102 is formed by, for example, a LOCOS (LOCal Oxidation of Silicon) method or a trench isolation method. In this embodiment, the trench isolation method is used to form thedevice isolation layer 102. After agate insulating layer 104 is formed on theactive region 101,gate structures 110 are formed on thegate insulating layer 104. - As a result, a recessed region is formed between each set of two adjacent gate structures. For example, for 0.18 micrometer devices, an upper width and a lower width of the recessed regions are 0.08 micrometers and 0.1 micrometers, respectively, and a height of the recessed regions is 0.4 micrometers.
- Formation of the
gate structures 110 includes depositing a conductive layer forgate electrodes 106 on thegate insulating layer 104. The conductive layer for thegate electrodes 106 is deposited to a thickness of about 2500 Å. In this embodiment, the conductive layer for thegate electrodes 106 is made of a multi-layer structure. Apolysilicon layer 106 a having a thickness of about 1000 Å, and asilicide layer 106 b having a thickness of about 1500 Å, are formed, in this order, over thegate insulating layer 104. A dielectric layer, also called a gate capping layer, which is used to create a gate capping mask 107, is deposited on the conductive layer for thegate electrodes 106. The dielectric layer for the gate capping mask 107 has an etch selectivity with respect to subsequentinter-layer dielectrics - The dielectric layer for the gate capping mask107 and the conductive layer for the
gate electrodes 106 are sequentially etched using a gate forming mask to form the gate capping mask 107 and thegate electrodes 106. Then impurity ions with low concentration are implanted into theactive region 101 at both sides of thegate electrodes 106 to form source/drain regions of low concentration. Alternatively, thegate electrodes 106 may be formed by etching the dielectric layer for the gate capping mask 107 to form a patterned layer, and thereafter etching the conductive layer using the patterned layer as the gate forming mask. - Next, a dielectric layer for the
gate spacers 108 may be deposited on thesubstrate 100. The dielectric layer for thegate spacers 108 may be made of silicon nitride, silicon oxide, silicon oxy-nitride, or a combination of these materials, such as in the gate capping mask 107, and is preferably made to a thickness in the range of about 300 Å to 1500 Å. The dielectric layer for thegate spacers 108 is preferably etched by an etch-back process to formgate spacers 108 on the side walls of a laminated layer which includes thegate electrode 106 and the gate capping mask 107. - If required, an
etch stopping layer 112 may be deposited over the resulting semiconductor structure (see alsoreference numeral 14 of FIG. 1A). Theetch stopping layer 112 is preferably made of silicon nitride deposited to a thickness in the range of 50 Å to 200 Å. Theetch stopping layer 112 is used to prevent thedevice isolation layer 102 and theactive region 101 from being etched during the step of etching the later formed dielectric between gate electrodes down to the top surface of the substrate to form an opening. - A
first inter-layer dielectric 114 is deposited over theetch stopping layer 112 such that it almost fills a recessed region betweenadjacent gate structures 110. Thefirst inter-layer dielectric 114 is preferably made of a silicon oxide such as BPSG, USG, PE-TEOS, HDP oxide, or a combination thereof. Thefirst inter-layer dielectric 114 is deposited to a thickness in the range of 300 Å to 3000 Å, preferably 2000 Å. If HDP oxide formed by a CVD method is used, an inert gas such as argon (Ar) or helium (He) may be used as a sputtering gas. - When the
first inter-layer dielectric 114 is formed using He gas as a sputtering gas, it can be deposited under the following conditions: a low frequency power (400 kHz) in the range of 2000 W to 4000 W, a high frequency power (13.56 MHz) in the range of 500 W to 3000 W, and using a process gas including silane (SiH4) gas with a flow rate in the range of 40 sccm to 120 sccm and O2 gas with a flow rate in the range of 40 sccm to 300 sccm. Preferably, the low frequency power is 3000 W, the high frequency power is 1300 W, the SiH4 gas has a flow rate of 80 sccm, and the O2 gas has a flow rate of 120 sccm. - When He gas having a flow rate in the range of 20 sccm to 600 sccm is used as a sputtering gas, the
first inter-layer dielectric 114 may have an improved deposition profile, as shown byreference numeral 115 in FIG. 2A. This is because re-sputtering of thefirst inter-layer dielectric 114 is low due to the fact that helium has an atomic mass of 4. - Next, the
inter-layer dielectric 114 is etched to leave part of theinter-layer dielectric 114 on the bottoms of the recessed regions between thegate structures 110, as shown in FIG. 2C. The etching process can be a wet etch. Wet etch is advantageously used because the space between adjacent recessed regions can be expanded further not only in a vertical direction, but also in a horizontal direction. The wet etch process may be performed by using a typical oxide etchant such as 200:1 HF, LAL (mixture of NH4F and HF), or BOE (buffered oxide etchant). - Alternatively, a dry etch process can be performed, or wet and dry etch processes can be performed by in-situ. The dry etch process is preferably performed by using an etch gas based on at least one material selected from the group consisting of Ar, CF4, CHF3, He, CH2F2, and O2. It should also be clear that the etching may be performed by using two separate wet etch processes. Alternatively, a combination of dry and wet etch processes can be employed.
- FIGS. 2B and 2C schematically show in detail the process of etching the
first inter-layer dielectric 114 using a combination of dry and wet etch processes, more particularly by first dry etching and then wet etching. - Referring now to FIG. 2B, part of the
first inter-layer dielectric 114 is removed by dry etching. The depth of the etching of thefirst inter-layer dielectric 114 is in the range of 150 Å to 500 Å, preferably 300 Å. The dry etching process can be performed with the following conditions. Both the low frequency power (400 kHz) and the high frequency power (13.56 MHz) preferably have a range of 2000 W to 4500 W. The etch gas may be helium gas, O2 gas, or a mixture thereof. Preferably, a mixture gas is used. When helium gas is used, it preferably has a flow rate of 390 sccm. When O2 gas is used, it preferably has a flow rate of 30 sccm. - As shown in FIG. 2B, after the dry etch process the profile of the
first inter-layer dielectric 114 is improved. Therefore, deposition of asecond inter-layer dielectric 116 can be performed immediately without performing a wet etch process. However, so as to increase the likelihood of a void-free inter-layer dielectric, it is desirable that a wet etch process be performed immediately after the dry etch process. - The wet etch process which is performed immediately after the dry etch process can be performed with the following conditions. The
first inter-layer dielectric 114 is etched in the range of 100 Å to 400 Å, preferably 200 Å, in depth. The wet etch process is then performed by using a typical oxide etchant such as 200:1 HF, LAL, or BOE. As a result of this wet etch process, as shown in FIG. 2C, a top surface of thesubstrate 100 is smoothed, and the recessed portion between gate electrodes has a low aspect ratio which provides a good surface topology for a later-formed second inter-layer dielectric. - Subsequently, as shown in FIG. 2D, a
second inter-layer dielectric 116 is deposited over thesubstrate 100, including thefirst inter-layer dielectric 114, to fill up the recessed regions. As a result, a voidfree inter-layer dielectric 118, a combination of the first and secondinter-layer dielectrics second inter-layer dielectric 116 can be made of the same material as that of thefirst inter-layer dielectric 114, such as an HDP oxide. Alternatively, thesecond inter-layer dielectric 116 can be made of a material different from that of thefirst inter-layer dielectric 114, such as USG or PE-TEOS. - The
second inter-layer dielectric 116 is deposited to a thickness in the range of 300 Å to 3000 Å, preferably 2800 Å. Deposition of thesecond inter-layer dielectric 116 can be performed under the following conditions. The low frequency power has a range of 2000 W to 4000 W and the high frequency power has a range of 500 W to 4000 W. As process gases, silane (SiH4) gas has a flow rate in the range of 40 sccm to 120 sccm and O2 gas has a flow rate in the range of 40 sccm to 300 sccm. As a sputtering gas, helium gas is used. Preferably, the low frequency power is 3000 W, the high frequency power is 2000 W, the flow rate of silane is 120 sccm, and the flow rate of helium is 390 sccm. - According to the first embodiment of the present invention, the aspect ratio of the recessed regions can be reduced because part of the
first inter-layer dielectric 114 is left behind in the recessed regions. Therefore, a void is not produced during the deposition of thesecond inter-layer dielectric 116. - Subsequently, the top surface of the
second inter-layer dielectric 116 is planarized by using an etch-back process or a CMP process. - Second Embodiment
- FIG. 3 is a cross-sectional view of a semiconductor substrate depicting a method of forming a dielectric layer in accordance with a second embodiment of the present invention. Referring to FIG. 3, a
pad oxide 202, apad nitride 204 a, and anHTO oxide 204 b are deposited sequentially on asemiconductor substrate 200 and then patterned by using a photolithography process which is well-known in this art. As a result, atrench etch mask 204 is formed which comprises thepad nitride 204 a and theHTO oxide 204 b. Thesubstrate 200 is etched using thetrench etch mask 204 to form atrench 206 therein. Thermal oxidation is then performed to form an oxide film on both sidewalls and the bottom of thetrench 206. - A first
trench isolation layer 208 is deposited over thesubstrate 200 including thetrench 206. The firsttrench isolation layer 208 is preferably made of USG or HDP oxide. - Next, the first
trench isolation layer 208 is etched so as to leave part of it on the bottom of thetrench 206. Thus, a void can be removed that may be formed during and after depositing the firsttrench isolation layer 208. The etching of the firsttrench isolation layer 208 is performed by a dry etch process, a wet etch process, or a combination of dry and wet etch processes. - A second
trench isolation layer 210 is deposited to fill up thetrench 206. The secondtrench isolation layer 210 can be made of the same material as that of the firsttrench isolation layer 208. Alternatively, the secondtrench isolation layer 210 can be made of a material different from that of the firsttrench isolation layer 208, such as PE-TEOS. As a result of depositing the secondtrench isolation layer 210, a void-freetrench isolation layer 212 is completely formed. - The processes of depositing the first and the second trench isolation layers208, 210 are preferably performed by using a sputtering gas such as argon gas or helium gas.
- Thus, a method of forming a dielectric layer has been described according to the present invention. While the invention is susceptible to various modifications and alternative forms, specific embodiments have been shown by way of example in the drawings and described in detail herein. However, it should be understood that the invention is not limited to the particular forms disclosed as these are to be regarded as illustrative, rather than restrictive. Rather, the invention covers all modifications, equivalents, alternatives, processes, and structures falling with the spirit and scope of the invention as defined in the appended claims. For example, the invention is applicable to all processes of filling up a recessed region, a narrow space, or a recessed portion with a material layer, such as a conductive layer, or a dielectric layer.
Claims (19)
1. A method of forming a void free dielectric layer on a semiconductor topology having recessed regions, the method comprising:
depositing a first dielectric layer over the semiconductor topology;
etching the first dielectric layer to leave a part of the first dielectric layer at bottom portions of the recessed regions; and
depositing a second dielectric layer over the semiconductor topology to fill up remainders of the recessed regions.
2. The method according to , wherein etching the first dielectric layer is performed by using a process selected from the group consisting of a dry etch process, a wet etch process, and a combination thereof.
claim 1
3. The method according to , wherein etching the first dielectric layer is performed by using a dry etching after a wet etching.
claim 1
4. The method according to , wherein each of the first and second dielectric layers comprises an HDP oxide formed by CVD.
claim 1
5. The method according to , wherein depositing the first dielectric layer is performed by using a first sputtering gas selected from the inert gas group consisting of argon (Ar) and helium (He), and depositing the second dielectric layer is performed by using a second sputtering gas selected from the inert gas group consisting of argon and helium.
claim 4
6. The method according to , wherein the dry etch process is performed by using a sputtering gas selected from the group consisting of argon and helium, and using oxygen gas as a process gas.
claim 2
7. The method according to , wherein etching the first dielectric layer is performed by using a wet etch process after a dry etch process.
claim 1
8. The method according to , wherein etching the first dielectric layer is performed by using two separate wet etch processes.
claim 1
9. A method of forming a dielectric layer in spaces between spaced apart gate lines with an insulating layer thereon, the gate lines being formed on a semiconductor substrate, the method comprising:
depositing a first inter-layer dielectric layer over the semiconductor substrate to fill the spaces;
etching the first inter-layer dielectric layer to leave a part of the first inter-layer dielectric on the spaces; and
depositing a second inter-layer dielectric layer over the semiconductor substrate to fill up the remainders of the spaces,
wherein each of the first and second inter-layer dielectric layers is made of a material having an etch selectivity with respect to the insulating layer.
10. The method according to , wherein the first and second inter-layer dielectric layers comprise silicon oxide and the insulating layer formed on the respective conductive structures comprises silicon nitride.
claim 9
11. The method according to , wherein etching the first inter-layer dielectric layer comprises a dry etching and a subsequent wet etching.
claim 9
12. The method according to , wherein the dry etching uses a gas comprising helium with a flow rate of about 390 sccm and oxygen with a flow rate of about 30 sccm, at a low and high frequency power of about 2000 W to 4500 W, and the wet etching uses an etchant selected from the group consisting of HF (200:1), LAL (mixture of HF and NH4F), and BOE (buffered oxide etchant).
claim 11
13. The method according to , wherein etching the first inter-layer dielectric layer comprises a dry etch process and a wet etch process.
claim 9
14. The method according to , wherein the first and second inter-layer dielectric layers comprise an HDP oxide formed by CVD.
claim 9
15. The method according to , further comprising depositing an etch stopper prior to the step of depositing a first inter-layer dielectric layer, wherein the etch stopper has an etching selectivity with respect to the first and second inter-layer dielectric layers.
claim 9
16. A method of forming a dielectric layer, comprising:
forming a trench in a semiconductor substrate by etching thereof, the trench defining a bottom portion and both sidewalls;
depositing a first dielectric layer over the substrate including the trench;
etching the first dielectric layer to leave part of the first dielectric layer on the bottom portion of the trench; and
depositing a second dielectric layer over the substrate to fill up the remainder of the trench.
17. A method of forming a dielectric layer, comprising:
depositing a first dielectric layer over a semiconductor substrate including a recessed region, the first dielectric layer being deposited by using helium gas as a sputtering gas;
dry etching the first dielectric layer to leave part of the first dielectric layer on a bottom of the recessed region; and
depositing a second dielectric layer over the semiconductor substrate to fill up a remainder of the recessed region with the second dielectric layer.
18. The method according to , wherein:
claim 17
depositing the first dielectric layer includes creating a plurality of voids in the first dielectric layer,
dry etching the first dielectric layer includes removing the plurality of voids and leaving enough of the first dielectric layer so that the aspect ratio of the recessed region is lowered, and
depositing the second dielectric layer is performed without creating any voids capable of creating a bridge between underlying electrodes.
19. The method according to , further comprising:
claim 18
depositing a gate insulating layer on the semiconductor substrate;
depositing a polysilicon layer on the gate insulating layer, the polysilicon layer having a thickness of about 1000 Å;
depositing a silicide layer on the polysilicon layer, the silicide layer having a thickness of about 1500 Å;
depositing a gate capping layer on the silicide layer, the gate capping layer comprising silicon nitride having a thickness of about 1500 Å, silicon oxide having a thickness of about 500 Å, and silicon oxy-nitride having a thickness of about 600 Å;
etching the gate capping layer, the silicide layer, and the polysilicon layer to form a gate capping mask and a gate electrode; and
forming gate spacers along the sidewalls of the gate capping mask and the gate electrode.
Applications Claiming Priority (4)
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KR19980031287 | 1998-07-31 | ||
KR98-31287 | 1998-07-31 | ||
KR99-15624 | 1999-04-30 | ||
KR1019990015624A KR100319185B1 (en) | 1998-07-31 | 1999-04-30 | Method for forming dielectric layer |
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US6337282B2 US6337282B2 (en) | 2002-01-08 |
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US (1) | US6337282B2 (en) |
JP (1) | JP4726273B2 (en) |
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Also Published As
Publication number | Publication date |
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KR20000011253A (en) | 2000-02-25 |
CN1244032A (en) | 2000-02-09 |
US6337282B2 (en) | 2002-01-08 |
JP2000077404A (en) | 2000-03-14 |
JP4726273B2 (en) | 2011-07-20 |
DE19935946B4 (en) | 2007-08-16 |
DE19935946A1 (en) | 2000-02-10 |
CN1146961C (en) | 2004-04-21 |
KR100319185B1 (en) | 2002-01-04 |
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