Classifications

• • 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
  • H01L21/02227—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process
  • H01L21/02252—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by plasma treatment, e.g. plasma oxidation of the substrate
• • 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
  • H01L21/02041—Cleaning
  • H01L21/02057—Cleaning during device manufacture
  • H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
• • 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
  • H01L21/02123—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
• • 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
  • H01L21/02227—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process
  • H01L21/0223—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate
  • H01L21/02233—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate of the semiconductor substrate or a semiconductor layer
  • H01L21/02236—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate of the semiconductor substrate or a semiconductor layer group IV semiconductor
  • H01L21/02238—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate of the semiconductor substrate or a semiconductor layer group IV semiconductor silicon in uncombined form, i.e. pure silicon
• • 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
  • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
  • H01L21/67005—Apparatus not specifically provided for elsewhere
  • H01L21/67011—Apparatus for manufacture or treatment
• • 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
  • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
  • H01L21/67005—Apparatus not specifically provided for elsewhere
  • H01L21/67011—Apparatus for manufacture or treatment
  • H01L21/67017—Apparatus for fluid treatment

Definitions

• Embodiments of the present invention generally relate to apparatus and methods for selectively oxidizing silicon.
• Oxidation of silicon is a fundamental technology to CMOS fabrication, dating back to the inception of the integrated circuit.
• the most common methods for oxidation of silicon rely on thermal processes in ambient of O 2 , H 2 O/H 2 , H 2 O/O 2 , O 2 /H 2 or combinations thereof.
• the hardware used to provide the silicon oxidation process in the IC manufacturing are batch thermal furnaces and RTP. In conventional oxidation systems and processes, high temperature (above 700°C) is required to provide the activation energy for the oxide growth on silicon or poly- silicon.
• Advanced integrated circuit fabrication requires a number of process steps where thin films of silicon oxide are grown on silicon or polysilicon structures.
• the oxidation process must be selective, such that other materials including tungsten are not oxidized.
• thermal processing in either an ambient of O 2 , H 2 O/H 2 , or H 2 O/O 2 at high temperature (greater than 700°C) is used to perform this oxidation processes.
• an apparatus for selective oxidation of exposed silicon surfaces can include a thermal processing chamber with a plurality of walls having a first inlet connection and a second inlet connection, wherein the plurality of walls define a processing region within the processing chamber, a substrate support within the processing chamber, a hydrogen source in fluid connection with the first inlet connection of the processing chamber, a heat source in connection with the hydrogen source, a remote plasma source in fluid connection with the second inlet connection of the processing chamber, and an oxygen source in fluid connection with the remote plasma source.
• the fluid connection can comprise tubing which comprises an inert material.
• a method for selective oxidation of non-metal surfaces can include positioning a substrate in a processing chamber, wherein the processing chamber is maintained at a temperature less than 800°C, flowing hydrogen into the processing chamber, generating a remote plasma comprising oxygen, flowing the remote plasma into the processing chamber, wherein the remote plasma mixes with the hydrogen gas to create an activated processing gas, and exposing the substrate to the activated gas.
• a method for selective oxidation of non-metal surfaces can include positioning a substrate in a processing chamber, wherein the processing chamber is maintained at a temperature less than 800°C, flowing hydrogen in proximity to a hot wire apparatus to generate activated hydrogen, flowing the activated hydrogen into the processing chamber, generating a remote plasma comprising oxygen, mixing the remote plasma with the hydrogen gas in the processing chamber to create an activated processing gas, exposing the substrate to the activated gas to oxidize a desired amount of silicon, wherein the activated gas oxidizes silicon surfaces and reduces metal surfaces, and cooling the substrate.
• Figure 1 is a schematic representation of a thermal processing chamber with a remote plasma source according to one embodiment.
• Figure 2 is a block diagram of a method of selective oxidation according to one embodiment.
• Figures 3A and 3B are graphical representations of selective oxidation and reduction achieved both with and without pre-baking.
• Embodiments of the present invention generally relate to methods of selective oxidation of silicon. Embodiments more specifically relate to the selective oxidation of silicon and the selective reduction of tungsten to remove native oxides.
• the selective oxidation of Si over tungsten is an important process to repair silicon oxide damage caused by ion implantation or reactive ion etching (RIE) around tungsten gate electrodes on SiO 2 dielectric in the advanced CMOS devices.
• RIE reactive ion etching
• the embodiments described here can be employed to selectively oxidize silicon over non- metals in a rapid thermal processing (RTP) chamber or thermal furnace by using a combination of remote plasma and thermal processing.
• RTP rapid thermal processing
• thermal furnace by using a combination of remote plasma and thermal processing.
• the reaction involves water vapor or combustion of hydrogen and oxygen delivered to the substrate at a high temperature and pressure.
• High temperature can cause tungsten whiskering, which is the formation of long crystalline structures from the tungsten which can be detrimental to device performance.
• using a lower temperature selective oxidation would be more favorable to overall device performance.
• Figure 1 is a RTP chamber with a remote plasma source according to one embodiment.
• the RTP chamber employed with embodiments of the present invention may be of any type which can heat and cool a substrate while maintaining atmospheric conditions around the substrate, such as the Centura thermal processing system or the Vantage RTP system, available from Applied Materials, Inc. located in Santa Clara, CA. It is envisioned that other thermal processing chambers, including chambers from other manufacturers, may be employed with embodiments of the present invention without diverging from the scope of the present invention.
• the RTP chamber can employ heating from resistive heat, such as a resistive heating element formed in a substrate support, from radiant heat, such as from a heat lamp, or from radiant energy, such as from a laser annealing system.
• resistive heat such as a resistive heating element formed in a substrate support
• radiant heat such as from a heat lamp
• radiant energy such as from a laser annealing system.
• the processing chamber 100 generally comprises a chamber body 101 defining a processing area 1 10 in which a substrate 102 may be thermally processed.
• the substrate 102 is positioned on a substrate support 1 12 which can help define the processing area 1 10.
• An energy source 103 is configured to direct radiant energy 105 towards the processing area 1 10.
• a sensor 108 is disposed in position to measure an attribute of components in the interior of the chamber body 101 .
• the sensor 108 is configured to measure temperature of the substrate 102 by obtaining and measuring radiant energy from the substrate 102.
• the sensor 108 may be connected to a system controller 109, which may be used to adjust the energy source 103 according to the measurement from the sensor 108.
• a remote plasma source 120 Connected with the processing chamber 100 is a remote plasma source 120.
• the remote plasma source employed with embodiments of the present invention may be of any type which can be used to form a remote plasma comprising at least oxygen, such as a Revolution III Remote RF Plasma Source available from MKS Instruments located in Andover, MA. It is envisioned that other remote plasma chambers, including chambers from other manufacturers, may be employed with embodiments of the present invention without diverging from the scope of the present invention.
• a remote plasma source 120 is fluidly coupled to the processing chamber 100 through a first tubing 122, which can be a line of sight tubing.
• An oxygen gas source 126 is also fluidly coupled to the remote plasma source 120, such as an inductively coupled remote plasma source.
• Further embodiments can include an inert gas source 128 coupled with the remote plasma source 120 so as to create an oxygen/inert gas plasma which can be delivered to the processing area 1 10 of the processing chamber 100.
• the first tubing 122 fluidly couples the remote plasma source 120 to the processing chamber 100.
• the term "line of sight" used herein is meant to convey a short distance between the remote plasma source 120 and the processing chamber 100 so as to minimize the possibility of radical recombination or adsorption onto the surface of the tubing.
• the first tubing 122 can comprise an inert material, such as sapphire, quartz, or other ceramic material, to prevent adsorption and/or recombination of the oxygen radicals provided by the remote plasma source 120.
• the first tubing 122 can be configured to provide a direct, short path for oxygen radicals generated in the remote plasma source 120 into the processing chamber 100.
• a hydrogen gas source 124 is connected to the processing chamber 100.
• the hydrogen gas source 124 delivers hydrogen gas to the processing area 1 10 where the hydrogen gas will be activated by the remote plasma comprising oxygen delivered from the remote plasma source 120.
• a hot wire apparatus 130 can optionally be positioned between the hydrogen gas source 124 and the processing chamber 100. In embodiments with the hot wire apparatus 130, the hydrogen gas can be flowed over a hot filament of the hot wire apparatus 130 which activates the hydrogen prior to delivering the hydrogen into the chamber. Further, the hot wire apparatus 130 can be be connected to the processing chamber using a second tubing 132, such as a line of sight tubing. The composition and parameters for the first tubing 122 can be used for the second tubing 132.
• Temperature control is important to the formation of silicon oxide while simultaneously not forming whisker structures on tungsten.
• the RTP chamber used in embodiments described herein should be able to control temperature between the ranges of 500°C and 1 100°C with fast heating and cooling of the substrate in the chamber. Such heating and cooling may be performed using structures, such as heating elements and/or coolant ports in the substrate support.
• FIG. 2 is a block diagram of a method of selective oxidation according to one embodiment.
• the method 200 can include positioning the substrate in a thermal processing chamber, wherein the substrate is maintained at a temperature less than 800°C, as in step 202.
• tungsten whiskers may form on tungsten features deposited on the surface of a substrate. As the tungsten whiskers grow, they can contact nearby features as well as creating a non-uniform surface of the substrate. Further, maintaining temperatures below about 800°C is beneficial for applications with a low thermal budget. Therefore, maintenance of the substrate at temperatures below about 800°C, and preferably at or below about 700°C, can be beneficial to the overall functionality of the semiconductor device.
• the method 200 can further include flowing hydrogen into the processing chamber, as in step 204.
• Silicon is difficult to oxidize by conventional thermal oxidation in O2 or H 2 O, usually requiring a very high temperature and long time. It is known to oxidize in atomic oxygen, including species generated by an oxygen plasma. The use of O 2 and H 2 mixtures, including O 2 activated by a plasma may also allow oxidation of silicon, while also changing the rate and/or the relative rates of oxidation of silicon and other materials, such as tungsten.
• the flow rates of H 2 can be from about 1 slm to about 10 slm (from about 3.33 sccm/cm 2 to about 33.33 sccm/cm 2 ).
• the hydrogen can be flowed into the chamber to maintain an overall chamber pressure of between 1 Torr and 2 Torr, such as 1 .5 Torr.
• the temperature of the substrate can be ramped down to between about 550°C and about 650°C, such as a substrate which is ramped down to about 600°C.
• the chamber can be maintained at the same temperature as the substrate.
• a further embodiment may include a pre-soak/pre-bake process.
• hydrogen (H 2 ) is flowed into a processing chamber with a substrate located therein.
• the substrate is then soaked in between about 450 Torr and about 550 Torr of H 2 , for example 530 Torr, while maintaining the substrate at about 700°C.
• the substrate then remains in the H 2 soak for a short period of time, such as between about 45 and about 75 seconds, such as 60 seconds.
• a pre- soak in H 2 may benefit the formation of silicon oxide while simultaneously reducing the native oxide formed on the surface of the tungsten.
• H 2 is flowed over a hot filament.
• the filament can be composed of a corrosion resistant metal or alloy, such as tungsten or ruthenium-tungsten.
• the hot filament can activate the hydrogen without forming a plasma, thereby preventing some of the more deleterious effects which can be seen when using hydrogen as a plasma.
• the activated hydrogen which will comprise H 2 and ionized hydrogen, is flowed into the processing chamber where the activated hydrogen can both extract oxygen from the native oxides formed on the surface of exposed metals, such as tungsten, and deposit oxygen onto the silicon. The reduction of tungsten has been seen from 70 atomic % to 95 atomic % hydrogen.
• the method 200 can further include generating a remote plasma comprising oxygen, as in step 206.
• a remote plasma comprising oxygen
• H 2 when converted to a plasma, can attack the source and other chamber components, such as components composed of anodized aluminum, quartz and sapphire. This reaction can lead to premature source failure. Further, the reaction with H 2 can create deposition precursors such as metal hydrides, which can deposit on the substrate.
• activated species of oxygen can be formed with minimal damage to the substrate and without having the deleterious effects of hydrogen plasma when contacting other portions of the chamber. Further, the activated oxygen can be used to activate the hydrogen in the presence of the substrate so as to limit the effects of the ionized/radicalized hydrogen to the substrate.
• the oxygen gas is flowed into the remote plasma source at from about 1 slm to about 5 slm for a 300cm 2 substrate (from about 3.33 sccm/cm 2 to about 16.67 sccm/cm 2 ).
• the oxygen gas can be mixed with an inert gas to form an oxygen gas mixture.
• the inert gas can include gases such as argon, helium or krypton. Either the oxygen gas or the mixture can then be converted to a plasma using an energy source.
• the energy source can be a capacitive, inductive or microwave energy source.
• the method 200 can further include flowing the remote plasma into the processing chamber, wherein the remote plasma mixes with the hydrogen gas to create an activated processing gas, as in step 208.
• the plasma can be either allowed to quench before flowing or flowed as a plasma into the chamber through the line of sight tube.
• the plasma is mixed with the hydrogen over the substrate, creating H, O and OH molecules.
• the temperature of the substrate is maintained between 550°C and 650°C, such as at 600°C, to benefit the formation of silicon oxides.
• the hydrogen which was flowed into the chamber in the pre-bake step may be reused as the hydrogen gas for the activated processing gas. Further embodiments can include clearing the chamber with an inert gas or hydrogen gas prior to flowing in hydrogen to create the activated gas. These steps can occur simultaneously with the formation of the oxygen plasma. As well, the hydrogen may be flowed into the chamber before the oxygen plasma is flowed from the remote plasma source or flowed simultaneously to mix with the oxygen plasma over the substrate. [0034] The method 200 can further include exposing the substrate to activated gas to oxidize the silicon and reduce exposed metals, such as tungsten, as in step 210.
• Plasma oxidation of silicon generally obeys an Arrhenius-like dependence with temperature, but with a much lower activation energy than thermal oxidation owing to the presence of oxygen radicals formed in the plasma. Due to the activation of the oxygen and subsequent or concurrent activation of the hydrogen, the silicon is oxidized. Further, the activated species of hydrogen and oxygen can lead to the reduction of tungsten under the same conditions.
• Figure 3A is experimental data showing increased silicon oxide growth on silicon substrates. All data was collected from 300mm bare silicon substrates. The substrates were initially heated to 700°C, followed by an optional pre-bake step.
• the optional pre-bake step includes a soak for 60 seconds in H 2 at a pressure of 530 Torr. After the pre-bake step, the temperature was ramped down to 600°C and the pressure was ramped to 1 .5 Torr. During the selective oxidation portion, the temperature was maintained at 600°C. Remote plasma was produced from oxygen with source power fixed at 3000W for 60 seconds and then flowed into the chamber where it was mixed with H 2 which is flowed separately in the chamber. The total pressure of H 2 and O 2 in the chamber was 1 .5 Torr.
• the graphical representation shows silicon oxide thickness from 80 atomic % to 100 atomic % H 2 .
• Silicon growth was higher between 80 atomic % and 90 atomic % hydrogen (with 20 atomic % and 10 atomic % oxygen respectively).
• between 70 atomic % and 95 atomic % hydrogen (with 30 atomic % and 5 atomic % oxygen respectively) provides optimal oxide growth on silicon.
• Silicon oxide thickness is consistently higher for pre-baked silicon substrates over the unbaked silicon substrate providing between 0.2A and 0.8A of increased thickness without the need for increased temperatures.
• the pre-bake silicon oxide is significantly higher in the 100% H 2 sample which may be oxide growth from sequestered oxygen redistributed by hydrogen in the presence of native oxides.
• Figure 3B is experimental data showing reduction of native tungsten oxides. All data was collected from 300mm silicon substrates with deposited tungsten by CVD processes. The substrates were initially heated to 700°C, followed by an optional pre-bake step. The optional pre-bake step includes a soak for 60 seconds in H 2 at a pressure of 530 Torr. After the pre-bake step, the temperature was ramped down to 600°C and the pressure was ramped to 1 .5 Torr. During the selective oxidation portion, the temperature was maintained at 600°C. Remote plasma was produced from oxygen with source power fixed at 3000W for 60 seconds and then flowed into the chamber where it was mixed with H 2 which is flowed separately in the chamber. The total pressure of H 2 and O 2 in the chamber was 1 .5 Torr.
• the graphical representation shows a general decrease in native tungsten oxide thickness in the presence of both hydrogen and oxygen, as compared to no oxygen.
• Oxide concentration was measured using X-ray photoelectron spectroscopy (XPS).
• the XPS measurement shows 38-39% Oxygen% in as-deposited tungsten (native WO x ).
• the decrease in native WO x content was higher between 80 atomic % and 90 atomic % hydrogen (with 20 atomic % and 10 atomic % oxygen respectively).
• between 70 atomic % and 95 atomic % hydrogen can be used for reduction of native WO x .
• native WOx is consistently lower for pre-baked tungsten coated substrates over the unbaked tungsten coated substrates, providing between 2% and 3% of oxide reduction without the need for increased temperatures.
• the pre-bake native WO x is lower in the 100% H 2 sample which evidences a benefit to the pre-bake process in overall native WO x reduction that behaves synergistically with the oxygen treatment.
• tungsten can form oxides by contact with the atmosphere, such as during transfer between chambers. These oxides can degrade the functionality and shorten the life of tungsten features formed on a substrate. As such, it is important to remove these defects. Therefore, the benefits of decreased native WO x formation can be achieved using the same process and conditions as are taught for low temperature silicon oxide production. Further, it is believed that the combination of reducing tungsten and oxidizing silicon by the same process may be further synergistic by sequestering oxygen from the native WO x layer and forming silicon oxide on the exposed silicon.
• Embodiments described herein relate to an apparatus and method of selectively oxidizing exposed silicon while reducing native WO x .
• the silicon oxide layer may be damaged by processes such as etching.
• as- deposited metals, such as tungsten contain native oxides which may be detrimental to device performance.
• the apparatus and methods described above can both reduce native oxide on the deposited metals while simultaneously forming silicon oxide from the exposed silicon, without temperatures over 800°C.

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