US20050073803A1 - Methods of manufacturing integrated circuit devices that include a metal oxide layer disposed on another layer to protect the other layer from diffusion of impurities and integrated circuit devices manufactured using same - Google Patents
Methods of manufacturing integrated circuit devices that include a metal oxide layer disposed on another layer to protect the other layer from diffusion of impurities and integrated circuit devices manufactured using same Download PDFInfo
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- US20050073803A1 US20050073803A1 US10/967,835 US96783504A US2005073803A1 US 20050073803 A1 US20050073803 A1 US 20050073803A1 US 96783504 A US96783504 A US 96783504A US 2005073803 A1 US2005073803 A1 US 2005073803A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier
- H01L27/04—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier the substrate being a semiconductor body
- H01L27/10—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier the substrate being a semiconductor body including a plurality of individual components in a repetitive configuration
- H01L27/105—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier the substrate being a semiconductor body including a plurality of individual components in a repetitive configuration including field-effect components
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L28/00—Passive two-terminal components without a potential-jump or surface barrier for integrated circuits; Details thereof; Multistep manufacturing processes therefor
- H01L28/40—Capacitors
- H01L28/55—Capacitors with a dielectric comprising a perovskite structure material
- H01L28/56—Capacitors with a dielectric comprising a perovskite structure material the dielectric comprising two or more layers, e.g. comprising buffer layers, seed layers, gradient layers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- 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
- H01L21/02172—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 at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
- H01L21/02175—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 at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
- H01L21/02178—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 at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing aluminium, e.g. Al2O3
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- 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
- H01L21/02225—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
- H01L21/0228—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 deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
- H01L21/31616—Deposition of Al2O3
- H01L21/3162—Deposition of Al2O3 on a silicon body
Definitions
- the present invention relates generally to methods of manufacturing integrated circuit devices and integrated circuit devices manufactured using same, and, more particularly, to reducing the diffusion of impurities, such as hydrogen, into integrated circuit device layers during manufacturing.
- Ferroelectric capacitors may be used in integrated circuit memory devices. Specifically, non-volatile integrated circuit memory devices often make use of the remnant polarization (P r ) phenomenon of a ferroelectric layer, which corresponds to the concept of a binary memory. Two materials that are commonly used to form ferroelectric layers are PZT(Pb(Zr, Ti)O 3 ) and SBT(SrBi 2 Ta 2 O 9 ).
- a potential problem in forming a capacitor dielectric layer using a ferroelectric material is that the ferroelectric characteristic of the material used for the capacitor dielectric layer maybe degraded during additional integration processes, which are performed after the formation of the ferroelectric capacitor. This potential problem is described in more detail hereinafter.
- an InterLayer Dielectric (ILD) process In manufacturing an integrated circuit memory device, the following processes are typically performed after the formation of a capacitor: 1) an InterLayer Dielectric (ILD) process, 2) an InterMetal Dielectric (IMD) process, and 3) a passivation process.
- impurities may be generated, such as hydrogen, which can degrade a capacitor dielectric layer.
- the generated hydrogen may immediately infiltrate the capacitor dielectric layer during the foregoing processes or the hydrogen may gradually infiltrate the capacitor dielectric layer after the hydrogen has been introduced into an ILD layer, an IMD layer, or a passivation layer. As a result, the P r of the ferroelectric dielectric layer may decrease.
- the dielectric layer of the capacitor may be degraded.
- silane (SiH 4 ) gas and oxygen (O 2 ) gas may be used.
- Hydrogen is generated as a by-product of the reaction between the silane gas and the oxygen gas. The generated hydrogen may immediately diffuse into the dielectric layer of the ferroelectric capacitor and degrade the dielectric layer, or may be introduced into an interlayer insulation layer formed from the ILD process and gradually degrade the capacitor dielectric layer.
- the P r value of the capacitor dielectric layer may decrease to an extent that the capacitor dielectric layer may lose its ferroelectric characteristics.
- a ferroelectric dielectric layer may be similarly degraded as a result of performing an IMD process for forming an intermetal insulation layer and/or performing a passivation process for forming a passivation layer.
- an integrated circuit device is manufactured by exposing at least a portion of an insulation layer that comprises oxygen to a metal precursor that is reactive with oxygen so as to form a metal oxide layer on the portion of the insulation layer.
- the metal oxide layer may reduce the diffusion of impurities, such as hydrogen, into the insulation layer, which may degrade the electrical characteristics of the insulation layer.
- Exposing the portion of the insulation layer to the metal precursor may comprise pulsing the metal precursor over the integrated circuit device for about 0.1 to 2 seconds at a flow rate of about 50 to 300 sccm, and then exposing the integrated circuit device to an inert gas for a duration of about 0.1 to 10 seconds and at a flow rate of about 50 to 300 sccm.
- the integrated circuit device may be thermally treated in an oxygen atmosphere using a rapid thermal processing apparatus or a furnace type thermal processing apparatus.
- the thermal treatment may be performed at a temperature of about 400 to 600° C. for a duration of about 10 seconds to 10 minutes.
- the metal precursor may comprise a gas selected from the following group of gases: TriMethyl Aluminum (TMA), DiMethylAluminum Hydride (DMAH), DiMethylEthylAmine Alane (DMEAA), TriIsoButylAluminum (TIBA), TriEthyl Aluminum (TEA), TaCl 5 , Ta(OC 2 H 5 ) 4 ,TiCl 4 , Ti(OC 2 H 5 ) 4 , ZrCl 4 , HfCl 4 , Nb(OC 2 H 5 ) 5 , Mg(thd) 2 , Ce(thd) 3 , and Y(thd) 3 , wherein thd is given by the following structural formula:
- the insulation layer may comprise a capacitor dielectric layer and/or may comprise a material selected from the following group of materials: TiO 2 , SiO 2 , Ta 2 O 5 , Al 2 O 3 , BaTiO 3 , SrTiO 3 , (Ba, Sr)TiO 3 , Bi 4 Ti 3 O 12 , PbTiO 3 , PZT((Pb, La)(Zr, Ti)O 3 ), and (SrBi 2 Ta 2 O 9 )(SBT).
- a second metal oxide layer may be disposed on the insulation layer and the first metal oxide layer to further reduce the diffusion of impurities, such as hydrogen, into the insulation layer due to subsequent integration processing operations.
- the second metal oxide layer may be formed by pulsing a second metal precursor over the integrated circuit device, exposing the integrated circuit device to an inert gas, pulsing oxygen gas over the integrated circuit device, and then exposing the integrated circuit device to an inert gas.
- the second metal oxide layer may be denser than the first metal oxide layer.
- FIGS. 1-4 are cross-section views that illustrate methods of manufacturing integrated circuit devices that include a metal oxide layer to reduce the diffusion of impurities and integrated circuit devices manufactured using same in accordance with various embodiments of the present invention
- FIG. 5 is a graph that illustrates a result of analyzing an integrated circuit device manufactured in accordance with an embodiment of the present invention using X-ray photoelectron spectroscopy (XPS); and
- FIG. 6 is a graph that illustrates remnant polarization values of ferroelectric dielectric layers in integrated circuit devices manufactured in accordance with embodiments of the present invention.
- a capacitor C is formed on a semiconductor substrate S.
- the capacitor C comprises a lower electrode 100 , a capacitor dielectric layer 110 , and an upper electrode 120 , which are sequentially stacked as shown.
- the semiconductor substrate S comprises a device isolation layer 130 for defining an active region; a field effect transistor T, which comprises a gate electrode 160 , an underlying gate oxide layer 140 interposed between the gate electrode 160 and the semiconductor substrate S, nitride spacers 150 disposed on the sidewalls of the gate electrode 160 , and source and drain regions 170 and 171 ; an interlayer insulation layer 180 on the device isolation layer 130 and the field effect transistor T; and a contact plug 190 formed in the interlayer insulation layer 180 and electrically connected to the source region 170 .
- a field effect transistor T which comprises a gate electrode 160 , an underlying gate oxide layer 140 interposed between the gate electrode 160 and the semiconductor substrate S, nitride spacers 150 disposed on the sidewalls of the gate electrode 160 , and source and drain regions 170 and 171 ; an interlayer insulation layer 180 on the device isolation layer 130 and the field effect transistor T; and a contact plug 190 formed in the interlayer insulation layer 180 and electrically connected to the source region 170 .
- the semiconductor substrate S may be prepared by conventional methods. Although not shown, other elements besides the above-mentioned elements may be provided on the semiconductor substrate S.
- an interface layer may be interposed between the interlayer insulation layer 180 and the lower electrode 100 , and between the contact plug 190 and the lower electrode 100 .
- the interface layer may include an adhesive layer and a diffusion-preventing layer, which are sequentially stacked.
- the adhesive layer may comprise a material layer for enhancing the adhesive strength between the interlayer insulation layer 180 and the diffusion preventing layer, and between the contact plug 190 and the diffusion preventing layer.
- the adhesive layer may be a transition metal layer (e.g., a Ti layer).
- the diffusion preventing layer may prevent a material layer formed on the interface layer from reacting with the contact plug 190 during subsequent processing and may also prevent the contact plug 190 from degrading due to the diffusion of oxygen during subsequent processing performed in an oxygen atmosphere.
- the diffusion-preventing layer may be a nitride layer (e.g., a TiN layer) of a transition metal.
- a capping insulation layer comprising a nitride layer may be formed on the surface of the gate electrode 160 .
- the lower electrode 100 and the upper electrode 120 may each be, for example, a metal layer, a conductive metal oxide layer, or a compound of a metal layer and a metal oxide layer.
- the metal layer may be, for example, a Pt layer, a Ir layer, a Ru layer, a Rh layer, a Os layer, or a Pd layer.
- the conductive metal oxide layer may be, for example, a IrO 2 layer, a RuO 2 layer, a (Ca, Sr)RuO 3 layer, or a LaSrCoO 3 layer.
- the lower electrode 100 may be a Pt layer
- the upper electrode 120 may be a double layer in which an IrO 2 layer and an Ir layer are sequentially stacked.
- the capacitor dielectric layer 110 may be a TiO 2 layer, a SiO 2 layer, a Ta 2 O 5 layer, a Al 2 O 3 layer, a BaTiO 3 layer, a SrTiO 3 layer, a (Ba, Sr)TiO 3 layer, a Bi 4 Ti 3 O 12 layer, a PbTiO 3 layer, a PZT((Pb, La)(Zr, Ti)O 3 ) layer, a (SrBi 2 Ta 2 O 9 )(SBT) layer, or a compound layer of two or more of the foregoing materials.
- FIG. 2 an enlarged view of portion II of FIG. 1 is shown in which a metal oxide layer, such as an Al 2 O 3 layer, is selectively formed on the capacitor dielectric layer 110 in accordance with embodiments of the present invention.
- the semiconductor substrate S is loaded in atomic layer deposition equipment (not shown) and is heated to a temperature of about 100-400° C., preferably, about 300° C., under a state in which the pressure of a reaction chamber is maintained at about 0.1-1 torr.
- a metal precursor gas as a pulsing gas, which is reactive with oxygen, and an inert gas as a purge gas.
- a metal precursor such as an aluminum precursor
- the aluminum precursor may be TriMethyl Aluminum (TMA), DiMethyLAluminum Hydride (DMAH), DiMethylEthylAmine Alane (DMEAA), TriIsoButylAluminum (TIBA), TriEthyl Aluminum (TEA), or a mixture of two or more of the foregoing gases.
- the pulsing time may be about 0.1-2 seconds and the pulsing flow rate may be about 50-300 sccm.
- the aluminum precursor is preferably pulsed together with a carrier gas such as argon gas.
- TaCl 5 or Ta(OC 2 H 5 ) 4 may be used as a tantalum precursor; TiCl 4 or Ti(OC 2 H 5 ) 4 may be used as a titanium precursor; ZrCl 4 may be used as a zirconium precursor; HfCl 4 may be used as a hafnium precursor; Nb(OC 2 H 5 ) 5 may be used as a niobium precursor; Mg(thd) 2 may be used as a magnesium precursor; Ce(thd) 3 may be used as a cerium precursor; and Y(thd) 3 may be used as a yttrium precursor.
- the structural formula of “thd” is as follows:
- the pulsed aluminum precursor is chemically or physically adsorbed by the surface of the semiconductor substrate S. Because the aluminum precursor is reactive with oxygen, it tends to change into an Al 2 O 3 layer at the adsorption interface when it is adsorbed by a material layer containing oxygen.
- the exposed surface of the capacitor dielectric layer 110 may chemically adsorb the aluminum precursor as structural atoms react with the oxygen contained in the capacitor dielectric layer 110 .
- an Al 2 O 3 layer 200 is selectively formed on the exposed surface of the capacitor dielectric layer 110 at an atomic layer level.
- the aluminum precursor that is chemically or physically adsorbed by the exposed portions of the upper and lower electrodes 120 and 100 generally does not change into a metal oxide layer.
- the upper and/or lower electrodes 120 or 100 include a conductive metal oxide layer, such as an IrO 2 layer, an Al 2 O 3 layer may be formed on the exposed portion of the conductive metal oxide layer at an atomic layer level.
- the surface of the semiconductor substrate S is purged using inert gas.
- the inert gas may be argon gas, and the purging time and flow rate of the inert gas may be about 0.5-10 seconds and about 50-300 sccm, respectively.
- the aluminum precursor chemically adsorbed by surfaces of the lower electrode 100 and the upper electrode 120 is generally not purged and mostly remains.
- the purge time and flow rate of the inert gas may be adjusted to substantially remove the metal precursor adsorbed by the surfaces of the upper electrode 120 and the lower electrode 100 .
- the aluminum precursor pulsing operation and the inert gas purging operation constitute a single cycle of the atomic layer deposition process.
- the cycle may be repeated until an Al 2 O 3 layer 200 ′ having a desired thickness is obtained.
- an aluminum precursor reacts with oxygen atoms contained in the capacitor dielectric layer 110 through diffusion so that the Al 2 O 3 layer 200 ′ is continuously formed on the capacitor dielectric layer 110 at an atomic layer level.
- the aluminum precursor is adsorbed by surfaces of the upper electrode 120 and the lower electrode 100 , and an Al 2 O 3 layer is generally not formed thereon.
- An aluminum precursor usually contains hydrogen atoms. Accordingly, during a process of selectively forming an Al 2 O 3 layer on the capacitor dielectric layer 110 , in accordance with embodiments of the present invention, the dielectric characteristics of the capacitor dielectric layer 110 may be degraded. In particular, when the capacitor dielectric layer 110 is formed of a ferroelectric material such as a PZT layer or a SBT layer, the ferroelectric characteristics of the capacitor dielectric layer 110 may be degraded due to diffusion of hydrogen contained in the aluminum precursor. For example, the remnant polarization value of the capacitor dielectric layer 110 may decrease.
- thermal treatment may be performed in an oxygen atmosphere after the Al 2 O 3 layer is formed on the capacitor dielectric layer 110 to a desired thickness.
- the thermal treatment may be performed in a rapid thermal processing apparatus or a furnace type thermal processing apparatus.
- the temperature may be about 400-600° C. and the treatment may be performed for about 10 seconds to about 10 minutes.
- an encapsulating layer 210 is formed on the surface of the semiconductor substrate S and the capacitor C.
- the encapsulating layer 210 may comprise a metal oxide and may prevent hydrogen from diffusing into the capacitor dielectric layer 110 during a subsequent InterLayer Dielectric (ILD) process, InterMetal Dielectric (IMD) process, and/or passivation process.
- the encapsulating layer 210 may have a density associated therewith that is greater than the density of the layer 200 ′. Because the semiconductor substrate S on which the encapsulating layer 210 is formed has the capacitor C on the surface thereof, it has a generally large surface topology. Accordingly, the encapsulating layer is preferably formed using an atomic layer deposition method.
- a single cycle for forming the encapsulating layer 210 as an Al 2 O 3 layer may comprise the following operations: 1) pulsing aluminum source gas over the surface of the semiconductor substrate S, 2) purging with inert gas, 3) pulsing oxygen source gas, and 4) purging with inert gas. The cycle is repeated until the encapsulating layer 210 reaches a desired thickness.
- One of the aluminum precursors discussed above may be used as the aluminum source gas.
- H 2 O gas, O 3 gas or N 2 O gas may be used as the oxygen source gas.
- Argon gas may be used as the inert gas.
- the pulsing time of the TMA gas may be about 0.1-2 seconds
- the pulsing time of the H 2 O gas may be about 0.1-2 seconds
- the purging time and flow rate of the argon gas may be about 1-10 seconds and about 50-300 sccm, respectively
- the temperature of the semiconductor substrate S may be about 300° C.
- an Al 2 O 3 layer is selectively formed on a capacitor dielectric layer 110 that may reduce diffusion of impurities into the dielectric layer 110 .
- the layer 200 ′ and the encapsulating layer 210 may comprise Ta, Ti, Zr, Mg, Ce, Y, Nb, Hf, Sr, or Ca.
- a metal precursor containing Ta, Ti, Zr, Mg, Ce, Y, Nb, Hf, Sr or Ca may be used in the aluminum precursor pulsing operation of the first embodiment.
- an integrated circuit devices comprises a semiconductor substrate S, a conductive region 220 , which contains little or no oxygen, an interlayer insulation layer 230 , which is disposed on the conductive region 220 and contains oxygen, and an opening 240 , which exposes the conductive region 220 .
- the conductive region 220 may be the upper or lower electrode of a capacitor, a gate electrode, a bit line, a word line, or the lower conductive line of a multi-layered interconnection layer.
- the interlayer insulation layer 230 may be a silicon oxide layer or a silicon oxynitride layer.
- a metal oxide layer 250 (e.g., an Al 2 O 3 layer) is selectively formed on the exposed surface of the interlayer insulation layer 230 using atomic layer deposition as discussed hereinabove with respect to FIGS. 1-3 .
- the oxide layer may comprise alternative metals, such as Ta, Ti, Zr, Mg, Ce, Y, Nb, Hf, Sr, or Ca.
- a thermal treatment may be performed in an oxygen atmosphere after the metal oxide layer 250 is selectively formed to enhance the dielectric characteristic of the metal oxide layer 250 .
- the metal oxide layer 250 When the metal oxide layer 250 is selectively formed exclusively on the exposed surface of the interlayer insulation layer 230 , the metal oxide layer 250 can inhibit substances that can degrade a semiconductor device by diffusing to structures below the metal oxide layer 250 during subsequent processes of forming material layer(s) on the interlayer insulation layer 230 . Examples of integrated circuit devices formed in accordance with embodiments of the present invention are described hereafter.
- a capacitor in which a Pt layer (a lower electrode), a PZT layer (a capacitor dielectric layer), and an Ir/IrO 2 layer (an upper electrode) were sequentially stacked, was formed on a semiconductor substrate. Thereafter, the semiconductor substrate was loaded in an atomic layer deposition apparatus, and a stabilizing step was performed such that the pressure of a chamber was maintained at about 0.1-1 torr, and the temperature of the semiconductor substrate was maintained at about 300° C. Next, an atomic layer deposition process cycle, as discussed above with respect to FIG. 2 , was repeated 100 times and a test sample was obtained. TMA gas was used as an aluminum precursor and the pulsing time in each cycle was about 0.1 second.
- Argon gas was used as a purge gas, and the purging time in each cycle was about 1 second.
- an X-ray photoelectron spectroscopy analysis was performed on the integrated circuit device to check whether an Al 2 O 3 layer was formed on the capacitor dielectric layer.
- the result of the analysis is shown in FIG. 5 .
- the horizontal axis denotes binding energy and the vertical axis denotes arbitrary intensity.
- an aluminum 2p peak (see III) indicating binding energy between aluminum and oxygen may be observed. Accordingly, these results indicate that an Al 2 O 3 layer was selectively formed on the capacitor dielectric layer of the sample.
- oxygen source gas was not pulsed, it can be inferred that the oxygen contained in the Al 2 O 3 layer was supplied by the capacitor dielectric layer.
- a capacitor pattern was formed on a semiconductor substrate as discussed hereinabove with respect to FIGS. 1-3 and a Sample 1 and a Sample 2 were separately manufactured. Thereafter, the following operations were sequentially performed on the Samples 1 and 2, and the remnant polarization values of their capacitor dielectric layers were measured after completion of each operation. The results of the measurements are shown in FIG. 6 .
- the horizontal axis denotes the operations performed on the Samples 1 and 2
- the vertical axis denotes the remnant polarization values.
- step A 1 an Al 2 O 3 layer was selectively formed on a capacitor dielectric layer as discussed hereinabove with respect to FIGS. 1-3 .
- the process conditions of step A 1 were approximately the same as those used in Example 1.
- step A 2 the semiconductor substrate was loaded in a rapid thermal processing apparatus and thermally treated for about 10 seconds at a temperature of about 700° C. in an oxygen atmosphere.
- step A 3 an Al 2 O 3 layer that encapsulates the capacitor pattern was formed as discussed hereinabove with respect to FIGS. 1-3 .
- TMA gas, H 2 O gas, and argon gas were used as the aluminum source gas, the oxygen source gas, and the purge gas, respectively.
- the pulsing time of the TMA gas was about 0.5 seconds.
- the pulsing time of the H 2 O gas was about 0.3 seconds.
- the purging time and purging flow rate of the argon gas were about 6 seconds and about 150 sccm, respectively.
- the temperature of the wafer was about 300° C.
- step B 1 a semiconductor substrate including a capacitor disposed thereon was loaded in a rapid thermal processing apparatus and thermally treated.
- the process conditions of step B 1 were the same as those of step A 2 .
- step B 2 an Al 2 O 3 layer was formed that encapsulates the capacitor.
- the process conditions of step B 2 were the same as those of step A 3 .
- the remnant polarization value of the capacitor dielectric layer in Sample 1 decreases a little after step A 1 due to the influence of the TMA gas and the H 2 O gas, which contain hydrogen.
- the remnant polarization value increases over the initial value after performing the rapid thermal process in an oxygen atmosphere in step A 2 .
- the remnant polarization value decreases a little after encapsulating the capacitor in step A 3
- the decreased remnant polarization value is almost the same as the initial value.
- the remnant polarization value of the capacitor dielectric layer in Sample 1 rarely decreased even though TMA gas and H 2 O gas, which contain hydrogen, were used in step A 3 .
- the remnant polarization value of the capacitor dielectric layer in Sample 2 increases over the initial value after performing a rapid thermal process in an oxygen atmosphere in step B 1 .
- the remnant polarization value greatly decreases with respect to Sample 1, however, after encapsulating the capacitor in step B 2 .
- Sample 1 is different from Sample 2 in that it has a selectively formed metal oxide layer that has been thermal-treated in an oxygen atmosphere.
- the remnant polarization value in Sample 1 did not decrease even though Sample 1 had undergone Step A 3 in which hydrogen-base gas was supplied. This suggests that the thermal-treated metal oxide layer effectively reduced the diffusion of hydrogen into the capacitor dielectric layer. Accordingly, the thermal-treated metal oxide layer may reduce diffusion of hydrogen into the capacitor dielectric layer in subsequent ILD, IMD, and passivation processes.
- a metal oxide layer may be selectively formed exclusively on an insulation layer containing oxygen.
- the degradation of a capacitor dielectric layer may be reduced, even if a source gas containing hydrogen is used.
- degradation of a capacitor dielectric layer due to diffusion of hydrogen during an ILD process, an IMD process, or a passivation process, which are performed after encapsulating the capacitor may be effectively reduced.
Abstract
Integrated circuit devices are manufactured by exposing at least a portion of an insulation layer that comprises oxygen to a metal precursor that is reactive with oxygen so as to form a metal oxide layer on the portion of the insulation layer. The metal oxide layer may reduce the diffusion of impurities, such as hydrogen, into the insulation layer, which may degrade the electrical characteristics of the insulation layer.
Description
- This application claims the benefit of Korean Patent Application No. 00-35708, filed Jun. 27, 2000, the disclosure of which is hereby incorporated herein by reference.
- 1. Field of the Invention
- The present invention relates generally to methods of manufacturing integrated circuit devices and integrated circuit devices manufactured using same, and, more particularly, to reducing the diffusion of impurities, such as hydrogen, into integrated circuit device layers during manufacturing.
- 2. Background of the Invention
- Ferroelectric capacitors may be used in integrated circuit memory devices. Specifically, non-volatile integrated circuit memory devices often make use of the remnant polarization (Pr) phenomenon of a ferroelectric layer, which corresponds to the concept of a binary memory. Two materials that are commonly used to form ferroelectric layers are PZT(Pb(Zr, Ti)O3) and SBT(SrBi2 Ta2O9).
- A potential problem in forming a capacitor dielectric layer using a ferroelectric material is that the ferroelectric characteristic of the material used for the capacitor dielectric layer maybe degraded during additional integration processes, which are performed after the formation of the ferroelectric capacitor. This potential problem is described in more detail hereinafter.
- In manufacturing an integrated circuit memory device, the following processes are typically performed after the formation of a capacitor: 1) an InterLayer Dielectric (ILD) process, 2) an InterMetal Dielectric (IMD) process, and 3) a passivation process. During these processes, impurities may be generated, such as hydrogen, which can degrade a capacitor dielectric layer. The generated hydrogen may immediately infiltrate the capacitor dielectric layer during the foregoing processes or the hydrogen may gradually infiltrate the capacitor dielectric layer after the hydrogen has been introduced into an ILD layer, an IMD layer, or a passivation layer. As a result, the Pr of the ferroelectric dielectric layer may decrease.
- For example, when an ILD process is used to form a silicon oxide interlayer insulation layer after a ferroelectric capacitor is formed on a semiconductor substrate, the dielectric layer of the capacitor may be degraded. In other words, in the process of forming a silicon oxide interlayer insulation layer using, for example, a plasma enhanced chemical vapor deposition (PECVD) method, silane (SiH4) gas and oxygen (O2) gas may be used. Hydrogen is generated as a by-product of the reaction between the silane gas and the oxygen gas. The generated hydrogen may immediately diffuse into the dielectric layer of the ferroelectric capacitor and degrade the dielectric layer, or may be introduced into an interlayer insulation layer formed from the ILD process and gradually degrade the capacitor dielectric layer. As a result, the Pr value of the capacitor dielectric layer may decrease to an extent that the capacitor dielectric layer may lose its ferroelectric characteristics. Unfortunately, a ferroelectric dielectric layer may be similarly degraded as a result of performing an IMD process for forming an intermetal insulation layer and/or performing a passivation process for forming a passivation layer.
- According to embodiments of the present invention, an integrated circuit device is manufactured by exposing at least a portion of an insulation layer that comprises oxygen to a metal precursor that is reactive with oxygen so as to form a metal oxide layer on the portion of the insulation layer. The metal oxide layer may reduce the diffusion of impurities, such as hydrogen, into the insulation layer, which may degrade the electrical characteristics of the insulation layer.
- Exposing the portion of the insulation layer to the metal precursor may comprise pulsing the metal precursor over the integrated circuit device for about 0.1 to 2 seconds at a flow rate of about 50 to 300 sccm, and then exposing the integrated circuit device to an inert gas for a duration of about 0.1 to 10 seconds and at a flow rate of about 50 to 300 sccm.
- In accordance with further embodiments of the present invention, the integrated circuit device may be thermally treated in an oxygen atmosphere using a rapid thermal processing apparatus or a furnace type thermal processing apparatus. The thermal treatment may be performed at a temperature of about 400 to 600° C. for a duration of about 10 seconds to 10 minutes.
- The metal precursor may comprise a gas selected from the following group of gases: TriMethyl Aluminum (TMA), DiMethylAluminum Hydride (DMAH), DiMethylEthylAmine Alane (DMEAA), TriIsoButylAluminum (TIBA), TriEthyl Aluminum (TEA), TaCl5, Ta(OC2H5)4,TiCl4, Ti(OC2H5)4, ZrCl4, HfCl4, Nb(OC2H5)5, Mg(thd)2, Ce(thd)3, and Y(thd)3, wherein thd is given by the following structural formula:
- The insulation layer may comprise a capacitor dielectric layer and/or may comprise a material selected from the following group of materials: TiO2, SiO2, Ta2O5, Al2O3, BaTiO3, SrTiO3, (Ba, Sr)TiO3, Bi4Ti3O12, PbTiO3, PZT((Pb, La)(Zr, Ti)O3), and (SrBi2Ta2O9)(SBT).
- A second metal oxide layer may be disposed on the insulation layer and the first metal oxide layer to further reduce the diffusion of impurities, such as hydrogen, into the insulation layer due to subsequent integration processing operations.
- The second metal oxide layer may be formed by pulsing a second metal precursor over the integrated circuit device, exposing the integrated circuit device to an inert gas, pulsing oxygen gas over the integrated circuit device, and then exposing the integrated circuit device to an inert gas. In accordance with particular embodiments of the present invention, the second metal oxide layer may be denser than the first metal oxide layer.
- Other features of the present invention will be more readily understood from the following detailed description of specific embodiments thereof when read in conjunction with the accompanying drawings, in which:
-
FIGS. 1-4 are cross-section views that illustrate methods of manufacturing integrated circuit devices that include a metal oxide layer to reduce the diffusion of impurities and integrated circuit devices manufactured using same in accordance with various embodiments of the present invention; -
FIG. 5 is a graph that illustrates a result of analyzing an integrated circuit device manufactured in accordance with an embodiment of the present invention using X-ray photoelectron spectroscopy (XPS); and -
FIG. 6 is a graph that illustrates remnant polarization values of ferroelectric dielectric layers in integrated circuit devices manufactured in accordance with embodiments of the present invention. - While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail. It should be understood, however, that there is no intent to limit the invention to the particular forms disclosed, but on the contrary, the invention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the claims. Like numbers refer to like elements throughout the description of the figures. It will also be understood that when an element, such as a layer, region, or substrate, is referred to as being “on” another element, it can be directly on the other element or intervening elements may be present. In contrast, when an element is referred to as being “directly on” another element, there are no intervening elements present.
- Referring to
FIGS. 1-3 , methods of manufacturing integrated circuit devices that include a metal oxide layer to reduce the diffusion of impurities and integrated circuit devices manufactured using same, in accordance with embodiments of the present invention, will now be described. As shown inFIG. 1 , a capacitor C is formed on a semiconductor substrate S. The capacitor C comprises alower electrode 100, a capacitordielectric layer 110, and anupper electrode 120, which are sequentially stacked as shown. The semiconductor substrate S comprises adevice isolation layer 130 for defining an active region; a field effect transistor T, which comprises agate electrode 160, an underlyinggate oxide layer 140 interposed between thegate electrode 160 and the semiconductor substrate S,nitride spacers 150 disposed on the sidewalls of thegate electrode 160, and source anddrain regions interlayer insulation layer 180 on thedevice isolation layer 130 and the field effect transistor T; and acontact plug 190 formed in theinterlayer insulation layer 180 and electrically connected to thesource region 170. - The semiconductor substrate S may be prepared by conventional methods. Although not shown, other elements besides the above-mentioned elements may be provided on the semiconductor substrate S. For example, an interface layer may be interposed between the
interlayer insulation layer 180 and thelower electrode 100, and between thecontact plug 190 and thelower electrode 100. The interface layer may include an adhesive layer and a diffusion-preventing layer, which are sequentially stacked. The adhesive layer may comprise a material layer for enhancing the adhesive strength between theinterlayer insulation layer 180 and the diffusion preventing layer, and between thecontact plug 190 and the diffusion preventing layer. For example, the adhesive layer may be a transition metal layer (e.g., a Ti layer). The diffusion preventing layer may prevent a material layer formed on the interface layer from reacting with thecontact plug 190 during subsequent processing and may also prevent thecontact plug 190 from degrading due to the diffusion of oxygen during subsequent processing performed in an oxygen atmosphere. For example, the diffusion-preventing layer may be a nitride layer (e.g., a TiN layer) of a transition metal. In addition, a capping insulation layer comprising a nitride layer may be formed on the surface of thegate electrode 160. - The
lower electrode 100 and theupper electrode 120 may each be, for example, a metal layer, a conductive metal oxide layer, or a compound of a metal layer and a metal oxide layer. The metal layer may be, for example, a Pt layer, a Ir layer, a Ru layer, a Rh layer, a Os layer, or a Pd layer. The conductive metal oxide layer may be, for example, a IrO2 layer, a RuO2 layer, a (Ca, Sr)RuO3 layer, or a LaSrCoO3 layer. For example, thelower electrode 100 may be a Pt layer, and theupper electrode 120 may be a double layer in which an IrO2 layer and an Ir layer are sequentially stacked. - The capacitor
dielectric layer 110 may be a TiO2 layer, a SiO2 layer, a Ta2O5 layer, a Al2O3 layer, a BaTiO3 layer, a SrTiO3 layer, a (Ba, Sr)TiO3 layer, a Bi4Ti3O12 layer, a PbTiO3 layer, a PZT((Pb, La)(Zr, Ti)O3) layer, a (SrBi2Ta2O9)(SBT) layer, or a compound layer of two or more of the foregoing materials. - Referring now to
FIG. 2 an enlarged view of portion II ofFIG. 1 is shown in which a metal oxide layer, such as an Al2O3 layer, is selectively formed on the capacitordielectric layer 110 in accordance with embodiments of the present invention. The semiconductor substrate S is loaded in atomic layer deposition equipment (not shown) and is heated to a temperature of about 100-400° C., preferably, about 300° C., under a state in which the pressure of a reaction chamber is maintained at about 0.1-1 torr. - An atomic layer deposition process is then performed using a metal precursor gas as a pulsing gas, which is reactive with oxygen, and an inert gas as a purge gas. In more detail, a metal precursor, such as an aluminum precursor, is pulsed over the surface of the semiconductor substrate S. The aluminum precursor may be TriMethyl Aluminum (TMA), DiMethyLAluminum Hydride (DMAH), DiMethylEthylAmine Alane (DMEAA), TriIsoButylAluminum (TIBA), TriEthyl Aluminum (TEA), or a mixture of two or more of the foregoing gases. The pulsing time may be about 0.1-2 seconds and the pulsing flow rate may be about 50-300 sccm. The aluminum precursor is preferably pulsed together with a carrier gas such as argon gas.
- Instead of using an aluminum precursor as the metal precursor for the atomic layer deposition process other gases may be used in accordance with embodiments of the present invention. For example, TaCl5 or Ta(OC2H5)4 may be used as a tantalum precursor; TiCl4 or Ti(OC2H5)4 may be used as a titanium precursor; ZrCl4 may be used as a zirconium precursor; HfCl4 may be used as a hafnium precursor; Nb(OC2H5)5 may be used as a niobium precursor; Mg(thd)2 may be used as a magnesium precursor; Ce(thd)3 may be used as a cerium precursor; and Y(thd)3 may be used as a yttrium precursor. The structural formula of “thd” is as follows:
- The pulsed aluminum precursor is chemically or physically adsorbed by the surface of the semiconductor substrate S. Because the aluminum precursor is reactive with oxygen, it tends to change into an Al2O3 layer at the adsorption interface when it is adsorbed by a material layer containing oxygen. In particular, the exposed surface of the
capacitor dielectric layer 110 may chemically adsorb the aluminum precursor as structural atoms react with the oxygen contained in thecapacitor dielectric layer 110. As a result, an Al2O3 layer 200 is selectively formed on the exposed surface of thecapacitor dielectric layer 110 at an atomic layer level. If, however, theupper electrode 120 and thelower electrode 100 do not contain oxygen atoms, then the aluminum precursor that is chemically or physically adsorbed by the exposed portions of the upper andlower electrodes lower electrodes - After selectively forming the Al2O3 layer 200 exclusively on the
capacitor dielectric layer 110 at an atomic layer level by pulsing the aluminum precursor, the surface of the semiconductor substrate S is purged using inert gas. The inert gas may be argon gas, and the purging time and flow rate of the inert gas may be about 0.5-10 seconds and about 50-300 sccm, respectively. When the surface of the semiconductor substrate S is purged with inert gas, the aluminum precursor, which has been physically adsorbed by surfaces of thelower electrode 100 and theupper electrode 120 and has not reacted with thecapacitor dielectric layer 110, is substantially discharged from the reaction chamber. The aluminum precursor chemically adsorbed by surfaces of thelower electrode 100 and theupper electrode 120 is generally not purged and mostly remains. In accordance with embodiments of the present invention, however, the purge time and flow rate of the inert gas may be adjusted to substantially remove the metal precursor adsorbed by the surfaces of theupper electrode 120 and thelower electrode 100. - The aluminum precursor pulsing operation and the inert gas purging operation constitute a single cycle of the atomic layer deposition process. The cycle may be repeated until an Al2O3 layer 200′ having a desired thickness is obtained. During succeeding cycles, an aluminum precursor reacts with oxygen atoms contained in the
capacitor dielectric layer 110 through diffusion so that the Al2O3 layer 200′ is continuously formed on thecapacitor dielectric layer 110 at an atomic layer level. The aluminum precursor is adsorbed by surfaces of theupper electrode 120 and thelower electrode 100, and an Al2O3 layer is generally not formed thereon. - An aluminum precursor usually contains hydrogen atoms. Accordingly, during a process of selectively forming an Al2O3 layer on the
capacitor dielectric layer 110, in accordance with embodiments of the present invention, the dielectric characteristics of thecapacitor dielectric layer 110 may be degraded. In particular, when thecapacitor dielectric layer 110 is formed of a ferroelectric material such as a PZT layer or a SBT layer, the ferroelectric characteristics of thecapacitor dielectric layer 110 may be degraded due to diffusion of hydrogen contained in the aluminum precursor. For example, the remnant polarization value of thecapacitor dielectric layer 110 may decrease. To improve the ferroelectric characteristics of thecapacitor dielectric layer 110 and to enhance the dielectric characteristic, such as the density of the Al2O3 layer, thermal treatment (illustrated by arrows) may be performed in an oxygen atmosphere after the Al2O3 layer is formed on thecapacitor dielectric layer 110 to a desired thickness. In accordance with embodiments of the present invention, the thermal treatment may be performed in a rapid thermal processing apparatus or a furnace type thermal processing apparatus. When the thermal treatment is performed in a rapid thermal processing apparatus, the temperature may be about 400-600° C. and the treatment may be performed for about 10 seconds to about 10 minutes. - Referring to
FIG. 3 , in accordance with embodiments of the present invention, after the Al2O3 layer 200′ is selectively formed exclusively on the surface of thecapacitor dielectric layer 110 as described above, anencapsulating layer 210 is formed on the surface of the semiconductor substrate S and the capacitor C. Theencapsulating layer 210 may comprise a metal oxide and may prevent hydrogen from diffusing into thecapacitor dielectric layer 110 during a subsequent InterLayer Dielectric (ILD) process, InterMetal Dielectric (IMD) process, and/or passivation process. In accordance with particular embodiments of the present invention, theencapsulating layer 210 may have a density associated therewith that is greater than the density of thelayer 200′. Because the semiconductor substrate S on which theencapsulating layer 210 is formed has the capacitor C on the surface thereof, it has a generally large surface topology. Accordingly, the encapsulating layer is preferably formed using an atomic layer deposition method. - A single cycle for forming the
encapsulating layer 210 as an Al2O3 layer may comprise the following operations: 1) pulsing aluminum source gas over the surface of the semiconductor substrate S, 2) purging with inert gas, 3) pulsing oxygen source gas, and 4) purging with inert gas. The cycle is repeated until theencapsulating layer 210 reaches a desired thickness. One of the aluminum precursors discussed above may be used as the aluminum source gas. H2O gas, O3 gas or N2O gas may be used as the oxygen source gas. Argon gas may be used as the inert gas. - In accordance with embodiments of the present invention, when TMA gas, H2O gas, and argon gas are used as the aluminum source gas, the oxygen source gas, and the inert gas, respectively, the pulsing time of the TMA gas may be about 0.1-2 seconds, the pulsing time of the H2O gas may be about 0.1-2 seconds, the purging time and flow rate of the argon gas may be about 1-10 seconds and about 50-300 sccm, respectively, and the temperature of the semiconductor substrate S may be about 300° C.
- In accordance with embodiments of the present invention discussed hereinabove, an Al2O3 layer is selectively formed on a
capacitor dielectric layer 110 that may reduce diffusion of impurities into thedielectric layer 110. Thelayer 200′ and theencapsulating layer 210 may comprise Ta, Ti, Zr, Mg, Ce, Y, Nb, Hf, Sr, or Ca. In this case, a metal precursor containing Ta, Ti, Zr, Mg, Ce, Y, Nb, Hf, Sr or Ca may be used in the aluminum precursor pulsing operation of the first embodiment. - With reference to
FIG. 4 , methods of manufacturing integrated circuit devices that include a metal oxide layer to reduce the diffusion of impurities and integrated circuit devices manufactured using same, in accordance with further embodiments of the present invention, will be described hereafter. As shown inFIG. 4 , an integrated circuit devices comprises a semiconductor substrate S, aconductive region 220, which contains little or no oxygen, aninterlayer insulation layer 230, which is disposed on theconductive region 220 and contains oxygen, and anopening 240, which exposes theconductive region 220. Theconductive region 220 may be the upper or lower electrode of a capacitor, a gate electrode, a bit line, a word line, or the lower conductive line of a multi-layered interconnection layer. Theinterlayer insulation layer 230 may be a silicon oxide layer or a silicon oxynitride layer. - Subsequently, a metal oxide layer 250 (e.g., an Al2O3 layer) is selectively formed on the exposed surface of the
interlayer insulation layer 230 using atomic layer deposition as discussed hereinabove with respect toFIGS. 1-3 . In accordance with embodiments of the present invention, the oxide layer may comprise alternative metals, such as Ta, Ti, Zr, Mg, Ce, Y, Nb, Hf, Sr, or Ca. A thermal treatment may be performed in an oxygen atmosphere after themetal oxide layer 250 is selectively formed to enhance the dielectric characteristic of themetal oxide layer 250. - When the
metal oxide layer 250 is selectively formed exclusively on the exposed surface of theinterlayer insulation layer 230, themetal oxide layer 250 can inhibit substances that can degrade a semiconductor device by diffusing to structures below themetal oxide layer 250 during subsequent processes of forming material layer(s) on theinterlayer insulation layer 230. Examples of integrated circuit devices formed in accordance with embodiments of the present invention are described hereafter. - A capacitor, in which a Pt layer (a lower electrode), a PZT layer (a capacitor dielectric layer), and an Ir/IrO2 layer (an upper electrode) were sequentially stacked, was formed on a semiconductor substrate. Thereafter, the semiconductor substrate was loaded in an atomic layer deposition apparatus, and a stabilizing step was performed such that the pressure of a chamber was maintained at about 0.1-1 torr, and the temperature of the semiconductor substrate was maintained at about 300° C. Next, an atomic layer deposition process cycle, as discussed above with respect to
FIG. 2 , was repeated 100 times and a test sample was obtained. TMA gas was used as an aluminum precursor and the pulsing time in each cycle was about 0.1 second. Argon gas was used as a purge gas, and the purging time in each cycle was about 1 second. After obtaining the sample through the above series of steps, an X-ray photoelectron spectroscopy analysis was performed on the integrated circuit device to check whether an Al2O3 layer was formed on the capacitor dielectric layer. The result of the analysis is shown inFIG. 5 . InFIG. 5 , the horizontal axis denotes binding energy and the vertical axis denotes arbitrary intensity. Referring toFIG. 5 , an aluminum 2p peak (see III) indicating binding energy between aluminum and oxygen may be observed. Accordingly, these results indicate that an Al2O3 layer was selectively formed on the capacitor dielectric layer of the sample. In particular, because oxygen source gas was not pulsed, it can be inferred that the oxygen contained in the Al2O3 layer was supplied by the capacitor dielectric layer. - A capacitor pattern was formed on a semiconductor substrate as discussed hereinabove with respect to
FIGS. 1-3 and aSample 1 and aSample 2 were separately manufactured. Thereafter, the following operations were sequentially performed on theSamples FIG. 6 . InFIG. 6 , the horizontal axis denotes the operations performed on theSamples -
Sample 1 - In step A1, an Al2O3 layer was selectively formed on a capacitor dielectric layer as discussed hereinabove with respect to
FIGS. 1-3 . The process conditions of step A1 were approximately the same as those used in Example 1. Thereafter, in step A2, the semiconductor substrate was loaded in a rapid thermal processing apparatus and thermally treated for about 10 seconds at a temperature of about 700° C. in an oxygen atmosphere. Next, in step A3, an Al2O3 layer that encapsulates the capacitor pattern was formed as discussed hereinabove with respect toFIGS. 1-3 . TMA gas, H2O gas, and argon gas were used as the aluminum source gas, the oxygen source gas, and the purge gas, respectively. The pulsing time of the TMA gas was about 0.5 seconds. The pulsing time of the H2O gas was about 0.3 seconds. The purging time and purging flow rate of the argon gas were about 6 seconds and about 150 sccm, respectively. The temperature of the wafer was about 300° C. -
Sample 2 - In step B1, a semiconductor substrate including a capacitor disposed thereon was loaded in a rapid thermal processing apparatus and thermally treated. The process conditions of step B1 were the same as those of step A2. Thereafter, in step B2, an Al2O3 layer was formed that encapsulates the capacitor. The process conditions of step B2 were the same as those of step A3.
- Referring now to
FIG. 6 , the remnant polarization value of the capacitor dielectric layer inSample 1 decreases a little after step A1 due to the influence of the TMA gas and the H2O gas, which contain hydrogen. The remnant polarization value, however, increases over the initial value after performing the rapid thermal process in an oxygen atmosphere in step A2. Although the remnant polarization value decreases a little after encapsulating the capacitor in step A3, the decreased remnant polarization value is almost the same as the initial value. The remnant polarization value of the capacitor dielectric layer inSample 1 rarely decreased even though TMA gas and H2O gas, which contain hydrogen, were used in step A3. - The remnant polarization value of the capacitor dielectric layer in
Sample 2 increases over the initial value after performing a rapid thermal process in an oxygen atmosphere in step B1. The remnant polarization value greatly decreases with respect toSample 1, however, after encapsulating the capacitor in step B2. -
Sample 1 is different fromSample 2 in that it has a selectively formed metal oxide layer that has been thermal-treated in an oxygen atmosphere. In contrast withSample 2, the remnant polarization value inSample 1 did not decrease even thoughSample 1 had undergone Step A3 in which hydrogen-base gas was supplied. This suggests that the thermal-treated metal oxide layer effectively reduced the diffusion of hydrogen into the capacitor dielectric layer. Accordingly, the thermal-treated metal oxide layer may reduce diffusion of hydrogen into the capacitor dielectric layer in subsequent ILD, IMD, and passivation processes. - Although the invention has been described with reference to exemplary embodiments, it will be apparent to one of ordinary skill in the art that modifications of the described embodiments may be made without departing from the spirit and scope of the invention. For example, principles of the present invention may be applied when selectively forming a metal oxide layer exclusively on the exposed surface of a gate oxide layer in a gate electrode pattern.
- According to embodiments of the present invention, a metal oxide layer may be selectively formed exclusively on an insulation layer containing oxygen. In particular, by encapsulating a capacitor of a semiconductor memory device using an atomic layer deposition method, in accordance with embodiments of the present invention, the degradation of a capacitor dielectric layer may be reduced, even if a source gas containing hydrogen is used. In addition, degradation of a capacitor dielectric layer due to diffusion of hydrogen during an ILD process, an IMD process, or a passivation process, which are performed after encapsulating the capacitor, may be effectively reduced.
- In concluding the detailed description, it should be noted that many variations and modifications can be made to the preferred embodiments without substantially departing from the principles of the present invention. All such variations and modifications are intended to be included herein within the scope of the present invention, as set forth in the following claims.
Claims (12)
1-13. (Canceled)
14. An integrated circuit device, comprising:
a capacitor that comprises a lower electrode layer, a dielectric layer on the lower electrode layer, and an upper electrode layer on the dielectric layer;
a first metal oxide layer that is disposed on an exposed portion of the dielectric layer and has a first density associated therewith; and
a second metal oxide layer that encapsulates the capacitor and the first metal oxide layer and has a second density associated therewith that is greater than the first density.
15. The integrated circuit device of claim 14 , wherein the first and second metal oxide layers each comprise an element selected from the group of elements consisting of: Al, Ta, Ti, Zr, Mg, Ce, Y, Nb, Hf, Sr, and Ca.
16. The integrated circuit device of claim 14 , wherein the dielectric layer comprises a material selected from the group of materials consisting of: TiO2, SiO2, Ta2O5, Al2O3, BaTiO3, SrTiO3, (Ba, Sr)TiO3, Bi4Ti3O12, PbTiO3, PZT((Pb, La)(Zr, Ti)O3), and (SrBi2Ta2O9)(SBT).
17. The integrated circuit device of claim 14 , wherein the first metal oxide layer is disposed on a sidewall of the dielectric layer and a portion of a surface of the dielectric layer that is adjacent to the upper electrode.
18. A method of manufacturing an integrated circuit device, comprising:
forming an insulation layer that comprises oxygen on a substrate; and
forming a first metal oxide layer on at least a portion of the insulation layer by exposing the at least a portion of the insulation layer to a first metal precursor that is reactive with the oxygen in the insulation layer.
19. The method of claim 18 , further comprising:
forming a lower electrode on the substrate; and
forming an upper electrode on the insulation layer;
wherein forming the insulation layer that comprises oxygen on the substrate comprises:
forming the insulation layer that comprises oxygen on the lower electrode.
20. The method of claim 19 , further comprising:
forming a second metal oxide layer on the substrate that encapsulates the lower electrode, the insulation layer, the first metal oxide layer, and the upper electrode.
21. The method of claim 20 , wherein forming the first metal oxide layer comprises:
pulsing the first metal precursor over the integrated circuit device; and
exposing the integrated circuit device to an inert gas.
22. The method of claim 21 , wherein forming the second metal oxide layer comprises:
pulsing a second metal precursor over the integrated circuit device;
exposing the integrated circuit device to an inert gas; then
pulsing oxygen gas over the integrated circuit device; then
exposing the integrated circuit device to an inert gas.
23. The method of claim 18 , further comprising:
thermally treating the integrated circuit device in an oxygen atmosphere using one of a rapid thermal processing apparatus and a furnace type thermal processing apparatus.
24. The method of claim 18 , further comprising:
forming a conductive region on the substrate, the insulation layer being disposed on the conductive region and the substrate;
forming an opening in the insulation layer so as to expose at least a portion of the conductive region; and
forming the first metal oxide layer on the at least a portion of the insulation layer while maintaining the exposed portion of the conductive region substantially devoid of the first metal oxide layer by exposing the at least a portion of the insulation layer and the exposed portion of the conductive region to the first metal precursor that is reactive with the oxygen in the insulation layer.
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US6821862B2 (en) | 2004-11-23 |
KR20020001264A (en) | 2002-01-09 |
JP2002093797A (en) | 2002-03-29 |
JP4145509B2 (en) | 2008-09-03 |
KR100351056B1 (en) | 2002-09-05 |
US20020001971A1 (en) | 2002-01-03 |
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