US20180076026A1 - Steam oxidation initiation for high aspect ratio conformal radical oxidation - Google Patents

Abstract

A substrate oxidation assembly includes: a chamber body defining a processing volume; a substrate support disposed in the processing volume; a plasma source coupled to the processing volume; a steam source fluidly coupled to the processing volume; and a substrate heater. A method of processing a semiconductor substrate includes: initiating conformal radical oxidation of high aspect ratio structures of the substrate comprising: heating the substrate; and exposing the substrate to steam; and conformally oxidizing the substrate. A semiconductor device includes a silicon and nitrogen containing layer; a feature formed in the silicon and nitrogen containing layer having an aspect ratio of at least 40:1; and an oxide layer on the face of the feature having a thickness in a bottom region of the silicon and nitrogen containing layer that is at least 95% of a thickness of the oxide layer in a top region.

Description

BACKGROUND
• Embodiments of the present invention generally relate to semiconductor device fabrication, and in particular to substrate oxidation chambers for conformal radical oxidation of high aspect ratio structures with steam oxidation initiation.
• The production of silicon integrated circuits has placed difficult demands on fabrication steps to increase the number of devices while decreasing the minimum feature sizes on a chip. These demands have extended to fabrication steps including depositing layers of different materials onto difficult topologies and etching further features within those layers. This is especially an issue in the manufacturing of next generation NAND flash memory. NAND is a type of non-volatile storage technology that does not require power to retain data. To increase memory capacity within the same physical space, a three-dimensional NAND (3D NAND) design has been developed. Such a design typically introduces alternating oxide layers and nitride layers which are etched to produce a desired structure having one or more faces extending substantially perpendicularly to the substrate. Such design considerations have moved the field from oxidation of relatively low aspect ratio structures, for example 10:1 aspect ratios, to high aspect ratio (HAR) structures, for example 40:1 or greater aspect ratios. Prior fabrication steps have included methods for filling gaps and trenches in HAR structures.
• 3D NAND flash structures are often coated with silicon nitride (SiN_x) layers that are to be oxidized conformally in HAR structures. 3D NAND flash structures may have high or ultra-high aspect ratios, for example, a 40:1 aspect ratio, between a 40:1 and a 100:1 aspect ratio, a 100:1 aspect ratio, or even greater than 100:1 aspect ratio. New fabrication steps are required to conformally deposit layers on the faces of HAR structures, rather than simply filling gaps and trenches. For example, forming layers conformally onto the face of a HAR structure may require slower deposition rates. “Conformally” generally refers to uniform and/or constant-thickness layers on faces of structures. In the context of HAR structures, “conformally” may be most relevant when discussing the thickness of oxidation on the structure faces that are substantially perpendicular to the substrate. A more conformal deposition can reduce material build up at the top of the structure. Such material build up may result in material prematurely sealing off the top of the trench between adjacent structures, forming a void in the trench. Unfortunately, slowing the deposition rate also means increasing the deposition time, which reduces processing efficiency and production rates.
• It would be beneficial to efficiently conformally oxidize HAR structures, examples of which include SiN_xlayers.
SUMMARY
• In one embodiment, a substrate oxidation assembly includes: a chamber body defining a processing volume; a substrate support disposed in the processing volume; a plasma source coupled to the processing volume; a steam source fluidly coupled to the processing volume; and a substrate heater.
• In one embodiment, a method of processing a semiconductor substrate includes: initiating conformal radical oxidation of high aspect ratio structures of the substrate comprising: heating the substrate; and exposing the substrate to steam; and conformally oxidizing the substrate.
• In one embodiment, a semiconductor device includes a silicon and nitrogen containing layer; a feature formed in the silicon and nitrogen containing layer having: a face substantially perpendicular to a substrate; a bottom region; a top region farther from the substrate than the bottom region; and an aspect ratio of at least 40:1; and an oxide layer on the face of the feature, the oxide layer having a thickness in the bottom region that is at least 95% of a thickness of the oxide layer in the top region.
BRIEF DESCRIPTION OF THE DRAWINGS
• So that the manner in which the above recited features of the present disclosure can be understood in detail, a more particular description of the disclosure, briefly summarized above, may be had by reference to embodiments, some of which are illustrated in the appended drawings. It is to be noted, however, that the appended drawings illustrate only exemplary embodiments and are therefore not to be considered limiting of its scope, may admit to other equally effective embodiments.
• FIG. 1A illustrates a substrate with one or more SiNx HAR structures that have been oxidized, resulting in Si2N2O and SiO2 layers.FIG. 1B illustrates generally uniform thickness of the Si2N2O layer across the face of the HAR structure.FIG. 1C illustrates the Si2N2O layer formed non-uniformly.
• FIG. 2 illustrates a graph of Conformality vs Temperature for SiN_xHAR structures.
• FIG. 3 illustrates a graph of SiO_xthickness as a function of square root of time for SiN_xHAR structures.
• FIG. 4 illustrates a substrate oxidation assembly according to embodiments of this invention.
• FIG. 5 illustrates a substrate oxidation assembly according to embodiments of this invention.
• FIG. 6 illustrates a method of substrate processing according to embodiments of this invention.
• To facilitate understanding, identical reference numerals have been used, where possible, to designate identical elements that are common to the figures. It is contemplated that elements and features of one embodiment may be beneficially incorporated in other embodiments without further recitation.
DETAILED DESCRIPTION
• A substrate oxidation assembly may include a plasma source, for example a remote plasma source (RPS), and a processing chamber designed to perform atomic oxygen radical (O) growth (e.g., conformal radical oxidation) in high aspect ratio (HAR) structures, for example trench capacitor dielectrics, gate dielectrics, and 3D NAND flash structures. In some embodiments, the substrate oxidation assembly may utilize steam, such as water (H₂O) steam, to initiate radical oxidation of silicon nitride (SiN_x) material. The substrate oxidation assembly may be designed to initiate a reaction to form silicon oxynitride (Si₂N₂O) as an intermediary to forming silica (SiO₂). In some embodiments, the substrate oxidation assembly may include an external steam source, for example an ex-situ H₂O steam source, such as an H₂O injector, an ultrapure H₂O injector, a catalytic steam generator, or a pyrogenic steam source. The steam source may be quartz lined. The steam source may be fluidly coupled to the processing chamber by a conduit, which may be quartz-lined. The plasma source may utilize an oxygen-containing gas such as a mixture of hydrogen (H₂) and oxygen (O₂) with H₂concentration in the range of about 5% to about 10%. In some embodiments, the plasma source may be a RPS, magnetron typed plasma source, a Modified Magnetron Typed (MMT) plasma source, a remote plasma oxidation (RPO) source, a capcitively coupled plasma (CCP) source, an inductively coupled plasma (ICP) source, or a toroidal plasma source.
• FIG. 1A illustrates asubstrate40 with one ormore HAR structures50, for example one or more SiN_xstructures that have been conformally oxidized, resulting in a conformal SiO₂layer60. Faces of theHAR structure50 may be substantially perpendicular to thesubstrate40. For example, faces of theHAR structure50 may be at an angle of at least 60° to thesubstrate40. InFIG. 1A, a Si₂N₂O layer55 is illustrated between theHAR structure50 and the SiO₂layer60 on each face of the HAR structures. Note that atrench65 remains between the SiO₂layers60 on each face of the HAR structure.Trench65 may provide access to the faces of the HAR structures, for example for gas transmission and/or reactant removal. As aspect ratio increases, surface area of the HAR structures and the depth of the trenches likewise increase. As would be understood by one of ordinary skill in the art with the benefit of this disclosure, conformal radical oxidation of the faces of the HAR structures may be hampered by O depletion, especially near the bottom of the HAR structures, for example inbottom region51.
• It is currently believed that thermally-activated oxygen (O₂) molecules are thermodynamically unfavorable for oxidizing SiN_xinto the intermediate phase, Si₂N₂O layer55. However, once the intermediate phase, Si₂N₂O layer55, is formed, atomic oxygen provides high oxide growth rate and conformality on HAR structures, such as 3D NAND HAR memory trenches. Due to mass and energy transport challenges, O and hydroxyl (OH) is thought to be less thermodynamically favored to oxidize SiN_xinto the intermediate phase, Si₂N₂O layer55. Once the intermediate phase, Si₂N₂O layer55, is formed as the intermediator, then SiO₂layer60 may thermally grow in the presence of atomic oxygen.
• Heretofore, it had been expected that oxidation of SiN_xin HAR structures at temperatures below about 800° C. would have close to 100% conformality. As illustrated inFIG. 1A, it is currently believed that an intermediate reaction produces an intermediate phase, Si₂N₂O layer55, which then reacts with O radicals to form the SiO₂layer60. Therefore, for conformal radical oxidation of theHAR structure50, the thickness of the Si₂N₂O layer55 should be generally uniform across the face of theHAR structure50, as illustrated inFIG. 1B. However, recent research indicates that a metastable species, such as H or OH, may not form or appear near the bottom oftrench65, thereby lengthening the incubation times for the intermediate reaction inbottom region51. For example, at a substrate temperature of about 700° C., in the presences of O₂, for HAR structures, the Si₂N₂O layer55 may form non-uniformly, as illustrated inFIG. 10.
• The conformality of layers on HAR structures can be measured as a ratio of the bottom thickness (measured inbottom region51, nearer to the substrate40) to the top thickness (measured intop region52, farther from the substrate40), and when multiplied by 100 may be referred to as the “bottom/top %”. In some experiments, the bottom/top % of the Si₂N₂O layer55 at a substrate temperature of about 700° C., as illustrated inFIG. 10, is about 90%. This can also be seen atpoint70 in the graph of Conformality vs Temperature inFIG. 2. It is also currently believed that, at substrate temperatures between about 750° C.-800° C., in the presence of O₂, for HAR structures, the rate of O₂depletion allows the Si₂N₂O layer55 to grow slowly near the top, providing for a bottom/top % of close to 100%. This generally establishes conformal regime80 (between about 750° C. and about 800° C.) inFIG. 2. It is also currently believed that, at higher substrate temperatures, such as 850° C. and above, in the presences of O2, for HAR structures, the rate of O₂depletion allows the Si₂N₂O layer55 to grow rapidly near the top, resulting in a bottom/top % of between about 80% to about 90%. This can be seen atpoint85 inFIG. 2.
• Recent research indicates that a metastable species, such as H or OH, may not form near the bottom oftrench65, thereby lengthening the incubation times for the intermediate reaction inbottom region51. It is currently believed that atomic oxygen has a high species lifetime in HAR structures. However, H radicals do not tend to have a long species lifetime. Therefore, H radicals are believed to carry-away nitrogen. In some embodiments, an ammonia (NH3) by-product may form.
• With this new understanding of the incubation period for the intermediate reaction, it should be appreciated that the rate of O₂depletion near the bottom may worsen as the aspect ratio increases. Therefore, even at substrate temperatures of about 800° C., it may be difficult or impossible to achieve conformal radical oxidation for higher aspect ratio structures. However, further raising the substrate temperature to improve the rate of O2 depletion may warp or otherwise damage HAR structures. Similar principles may be applicable to crystalline silicon (polysilicon), and aluminum oxide HAR structures.
• As illustrated inFIG. 3, the incubation period for the intermediate reaction may decrease in the presence of steam. The data presented inFIG. 3 shows atline90 the SiO_xthickness as a function of square root of time for SiN_xHAR structures at 700° C. substrate temperature in the presence of 5% H₂plasma, for example, during RPO. Theline90 crosses the x-axis at just under 5 s^1/2, indicating the initial growth of SiO_x. However, for the same SiN_xHAR structures in the presence of 33% H₂and O radicals (as would be the case with steam),line95 crosses the x-axis at about 2.5 s^1/2. Consequently, it can be inferred that the incubation period for the intermediate reaction favors steam, while the growth of the oxide layer following the intermediate reaction favors oxygen. Thermodynamic calculations suggest that steam is a preferable reactant to form NH₃as by-product. O or OH is less favorable to form Si₂N₂O.
• FIG. 4 illustrates asubstrate oxidation assembly100, having achamber body105 and aplasma source110. Thesubstrate oxidation assembly100 may include, for example, a 3D NAND oxidation chamber.Plasma source110 may be a RPS. Thesubstrate oxidation assembly100 may include, for example, a MMT plasma reactor, a RPO reactor, a CCP reactor, an ICP reactor, or a toroidal source plasma immersion ion implantation reactor. Thesubstrate oxidation assembly100 may include, additionally or instead, the plasma sources associated with each of the reactors above. Thechamber body105 may define aprocessing volume115. Thechamber body105 may enclose a processing volume in which O and OH are used to process substrates, and the pressure of the processing volume may be maintained between about 0.5 Torr and 1 Torr to allow for plasma expansion and/or for uniform oxidation at the substrate. In some embodiments, the pressure may be maintained between about 10 mTorr and about 500 mTorr. In some embodiments, the pressure may be maintained between about 1 Torr and about 5 Torr. Theplasma source110 may utilize an oxygen-containinggas source130, such as a mixture of H₂and O₂, with a concentration of H₂in the range of about 5% to about 10%. In some embodiments, the gas provided by thegas source130 can be, for example, a gas that provides H₂and, optionally, other essentially non-reactive elements, such as nitrogen or the like. Theplasma source110 may operate at a power of about 5 kW. Thechamber body105 may have a total volume of between about 30 liters and about 60 liters. The diameter of the cross-sectional area of the chamber may be about 20 inches. In one embodiment,plasma source110 may be coupled to thechamber body105 through a gas port to supply reactive plasma from theplasma source110 through agas distributor120, such as a shower head, to theprocessing volume115.Gas distributor120 may have, for example, one or more outlet ports facingsubstrate support140. It is noted that theplasma source110 may be coupled to thechamber body105 in any suitable position to supply a reactive plasma to a substrate as needed.
• Thechamber body105 may contain asubstrate support140 disposed in theprocessing volume115. Thesubstrate support140 may include any technically feasible apparatus for supporting a substrate during processing. Thechamber body105 may contain a substrate heater. For example, in some embodiments, thesubstrate support140 is in contact with one or more heating elements150 (or arrays of heating elements) for conductive heating of the substrate during processing. Theheating elements150 may be electric resistance heating devices, inductive heating devices, or hot fluid conduits. In some embodiments,chamber body105 contains one or more lamps155 (or arrays of lamps) for radiative heating of the substrate during processing. In some embodiments, theheating elements150 and/orlamps155 may heat the substrate support to a temperature range of between about 700° C. and about 900° C. Temperature may be controlled through sensors (not shown) disposed in thechamber body105 and connected to a temperature controller (not shown) that varies power to the substrate heater. Thesubstrate support140 may have a cross-sectional area of about 70 mm². Thesubstrate support140 may be sized to provide a “rim” around the edge of a substrate. For example, thesubstrate support140 may be circular and have a diameter of about 300 mm. In some embodiments, thesubstrate support140 may have a diameter between about 10 mm to about 40 mm larger than that of an expected substrate. Likewise,heating elements150 may be sized to provide a larger cross-sectional area than thesubstrate support140. In some embodiments,heating elements150 may be circular and have a diameter of between about 320 mm and about 350 mm. Theplasma source110 may be arranged to be coaxial with aline142 perpendicular to, and through a center of, a substrate supporting surface of thesubstrate support140, which may be called an “axis” of thesubstrate support140. Likewise, thegas distributor120 may be arranged to be coaxial with theaxis142 of thesubstrate support140. Aplasma volume125 may be defined between thegas distributor120 and thesubstrate support140 in theprocessing volume115. Theplasma volume125 may be coupled to theplasma source110. The components of thesubstrate oxidation assembly100 may be arranged to allow for gas diffusion across the surface of the substrate facing away from thesubstrate support140. For example, the gas may enter theprocessing volume115 at a point along theaxis142 of the substrate support, and between about 5 inches to about 6 inches away from (e.g., above) the substrate surface. The gas may thereby flow across the surface of a substrate on thesubstrate support140.
• FIG. 5 illustrates asubstrate oxidation assembly200 with achamber body205, aplasma source210, and asteam source260, such as an ex-situ H₂O steam source. Unless otherwise stated,substrate oxidation assembly200 is configured similarly tosubstrate oxidation assembly100. Thechamber body205 may enclose aprocessing volume215, and asubstrate support240 may be disposed in theprocessing volume215. Theplasma source210 may be coupled to an oxygen-containinggas source230, which may contain a mixture of H₂and O₂with a concentration of H₂in the range of about 5% to about 10%. In some embodiments, thechamber body205 may include agas distributor220, such as a shower head.Gas distributor220 may have, for example, one or more outlet ports facingsubstrate support240. Aplasma volume225 may be between thegas distributor220 and thesubstrate support240 in theprocessing volume215. Theplasma volume225 may be coupled to theplasma source210 for forming a plasma in, or providing a plasma to, theplasma volume225. Thechamber body205 may enclose a substrate heater, for example in theprocessing volume215. In some embodiments, thesubstrate support240 includes one or more heating elements250 (or arrays of heating elements) for conductive heating of the substrate during processing. In some embodiments,chamber body205 encloses one or more lamps255 (or arrays of lamps) for radiative heating of the substrate during processing.
• Steamsource260 may be an external steam source, for example, an H₂O injector, an ultrapure H₂O injector, a catalytic steam generator, or a pyrogenic steam source. Thesteam source260 may be quartz-lined. In some embodiments, thesteam source260 may be fluidly coupled to theprocessing volume215 by a conduit, which may be quartz-lined. Steamsource260 may be fluidly coupled to theprocessing volume215 to distribute steam across the surface of thesubstrate support240 and/or around theaxis142 of thesubstrate support240. In some embodiments, the steam may be distributed symmetrically around theaxis142 of thesubstrate support240. Thesteam source260 is coupled to an inlet ofchamber body205, and theplasma volume225 may be between the inlet and thesubstrate support240. In some embodiments,steam source260 may be fluidly coupled togas distributor220. For example,gas distributor220 may have one or more inlet ports, andsteam source260 may fluidly couple to the one or more inlet ports. In some embodiments, thesteam source260 may be a catalytic steam generator. The catalytic steam generator may generate ultra-high purity H₂O vapor by means of a catalytic reaction of O₂and H₂. The catalytic steam generator may generate the vapor at low temperatures (e.g., <500° C.) by exposing a hydrogen source gas, for example H₂, and an oxygen source gas, for example O₂, to a catalyst. The catalytic steam generator may have a catalyst-lined reactor or a catalyst cartridge in which H₂O vapor is generated by means of a chemical reaction. The catalyst contained within a catalyst reactor may include a metal or alloy, such as palladium, platinum, nickel, iron, chromium, ruthenium, rhodium, alloys thereof or combinations thereof. Regulating the flow of hydrogen source gas and oxygen source gas may allow the concentration to be precisely controlled at any point from 1% to 100% concentrations. In some embodiments, the ratio of O₂to H₂is between about 14:20 to about 21:20, or about 21:20. The H₂O vapor may contain H₂O, H₂, O₂and combinations thereof. In some embodiments, the steam may contain at least 30% H₂. In some embodiments, the concentration of components of the steam and any carrier gas are selected to reduce the presence of O in the processing volume during the incubation period. In some embodiments, thesteam source260 may be a pyrogenic generator. The pyrogenic generator may produce H₂O vapor as a result of ignition, often at temperatures over 1,000° C.
• In some embodiments, substrates having HAR structures may be loaded into a chamber body in the presence of nitrogen. The substrates may be initially heated by a substrate heater. During the initial heating, the substrate may be exposed to oxygen, nitrogen, or a combination thereof. In some embodiments, the substrate heater may be a conductive heater, such as a resistive heater, in contact with a substrate support. The conductive heater may operate in a temperature range of between about 700° C. and about 900° C. In some embodiments, the substrate heater may be a radiative heater, such as one or more lamps directed at the substrate. It should be apparent that the substrate temperature may be somewhat less than that of the substrate heater. For example, the substrate temperature may be cooler than the substrate heater by about 100° C. to about 200° C. In some embodiments, the substrate temperature may be between about 500° C. and about 700° C., even after 60 seconds or more of heating. In some embodiments, after the initial heating the substrate temperature may be between about 750° C. and about 800° C. In some embodiments, the walls of the chamber body may be maintained at a temperature around 50° C. The initial heating may proceed for a predetermined time (e.g., between about 60 seconds and 120 seconds) and/or until a measurement of substrate temperature returns a desired reading. For example, initial heating may proceed until the substrate temperature measures to be at least 600° C. The substrate temperature may be measured, for example, by a pyrometer or a quartz thermocouple.
• Once the initial heating has been completed, steam oxidation may initiate conformal radical oxidation of the substrate. Steam may be introduced into the chamber body. Steam may be introduced in combination with a carrier gas, for example O₂or an inert gas, such as nitrogen or argon. Steam may be introduced at a partial pressure of about 50 Torr or less. The substrate heater may continue to heat the substrate during the steam exposure. The substrate may be exposed to steam for a predetermined time (e.g., between about 5 seconds and about 45 seconds). The steam may initiate an intermediate reaction on the face of the HAR structures. For example, Si₂N₂O may form on the face of the SiN_xstructures in the presence of steam. In some embodiments, Si₂N₂O may form conformally on the face of the SiN_xstructures in the presence of steam.
• Once the steam exposure has been completed, the chamber body may be purged. The substrate may then be exposed to plasma, for example from a RPS. The substrate heater may continue to heat the substrate during the plasma exposure. The plasma may conformally oxidize the HAR structures. For example, SiO₂may form on the face of the SiN_xstructures in the presence of plasma. A layer of Si₂N₂O may remain between the face of the SiN_xstructures and the SiO₂.
• As illustrated inFIG. 6, amethod300 is described with respect to the illustrative structures depicted inFIGS. 4 and 5. Themethod300 generally begins atstep305, by enclosing a substrate having HAR structures in a chamber body. The substrate may include any material suitable for fabrication of the type of memory device (e.g., a 3D NAND flash memory device) identified above, for example, such as crystalline silicon, strained silicon, silicon germanium, doped or undoped polysilicon, doped or undoped silicon wafers, patterned or non-patterned wafers, silicon on insulator (SOI), carbon doped silicon oxides, doped silicon, or the like. Themethod300 may then include, atstep310, initially heating the substrate. In some embodiments,step310 may be skipped, and themethod300 may proceed directly to step320, flowing steam into the chamber body for a time period, for example, between about 5 seconds and about 45 seconds. The time period may decrease as the temperature of the substrate increases. The steam may be generated externally to a chamber body in which the substrate is disposed. The steam may then be flowed into the chamber body and/or across the surface of the substrate. While the steam is flowing, the pressure in the chamber may be between about 0.5 Torr and about 100 Torr. The steam may be mixed with a carrier gas, for example O₂or an inert gas, such as nitrogen or argon. The steam may initiate an intermediate reaction on the face of the HAR structures. For example, atstep321 the Si₂N₂O may form on the face of the SiN_xstructures in the presence of steam. The substrate may be heated atstep322 while the steam is flowing. Optionally, the method may include atstep325 purging the chamber following flowing the steam. The method may then include atstep330 flowing plasma into the chamber body for a time period. The plasma may flow from a plasma source, such as a RPS, coupled to a precursor gas source. The plasma may include O₂at a concentration of about 95% and H at a concentration of about 5%. The pressure of the plasma may be about 1 Torr to about 5 Torr. The plasma may conformally oxidize the HAR structures. For example, atstep331 SiO₂may form on the face of the SiN_xstructures in the presence of plasma.
• In one embodiment, a substrate oxidation assembly includes: a chamber body defining a processing volume; a substrate support disposed in the processing volume; a plasma source coupled to the processing volume; a steam source fluidly coupled to the processing volume; and a substrate heater.
• In one or more embodiment disclosed herein, the substrate oxidation assembly further includes a quartz-lined conduit fluidly coupling the steam source to the processing volume.
• In one or more embodiment disclosed herein, the steam source is quartz-lined.
• In one or more embodiment disclosed herein, the processing volume includes a plasma volume, and the plasma source is coupled to the plasma volume.
• In one or more embodiment disclosed herein, the steam source is coupled to an inlet of the chamber body, and the plasma volume is between the inlet and the substrate support.
• In one or more embodiment disclosed herein, the substrate oxidation assembly further includes a gas distributor coupled to the chamber body, wherein: the gas distributor has one or more inlet ports, the steam source is fluidly coupled to the one or more inlet ports, and the gas distributor has one or more outlet ports facing the substrate support.
• In one or more embodiment disclosed herein, the processing volume includes a plasma volume, the plasma source is coupled to the plasma volume; and the plasma volume is between the gas distributor and the substrate support.
• In one or more embodiment disclosed herein, the substrate oxidation assembly further includes a gas distributor coupled to the chamber body, wherein: the gas distributor has one or more inlet ports, and the steam source is fluidly coupled to the one or more inlet ports by a quartz-lined conduit.
• In one or more embodiment disclosed herein, the plasma source includes at least one of a remote plasma source, magnetron typed plasma source, a Modified Magnetron Typed plasma source, a remote plasma oxygen source, a capcitively coupled plasma source, an inductively coupled plasma source, and a toroidal plasma source.
• In one or more embodiment disclosed herein, the substrate oxidation assembly further includes an oxygen-containing gas source fluidly coupled to the plasma source.
• In one or more embodiment disclosed herein, the oxygen-containing gas contains 5% to 10% hydrogen.
• In one or more embodiment disclosed herein, the steam source includes at least one of an H₂O injector, an ultrapure H₂O injector, a catalytic steam generator, and a pyrogenic steam source.
• In one or more embodiment disclosed herein, the substrate oxidation assembly further includes at least one of a radiative heating source and a conductive heating source operatively coupled to the substrate support.
• In one or more embodiment disclosed herein, the substrate heater is capable of heating to between 700° C. and 1100° C.
• In one or more embodiment disclosed herein, the chamber is capable of conformal radical oxidation of high aspect ratio structures.
• In one or more embodiment disclosed herein, after conformal radical oxidation, a thickness of a silicon dioxide layer in a bottom region of the high aspect ratio structures is between 95% and 105% of a thickness of a silicon dioxide layer in a top region of the high aspect ratio structures.
• In one or more embodiment disclosed herein, the high aspect ratio structures have an aspect ratio of at least 40:1.
• In one or more embodiment disclosed herein, the high aspect ratio structures comprise at least one of silicon nitride, crystalline silicon, or aluminum oxide.
• In one or more embodiment disclosed herein, the high aspect ratio structures comprise 3D NAND structures.
• In one embodiment, a method of processing a semiconductor substrate includes: initiating conformal radical oxidation of high aspect ratio structures of the substrate comprising: heating the substrate; and exposing the substrate to steam; and conformally oxidizing the substrate.
• In one or more embodiment disclosed herein, the method further includes, before the initiating conformal radical oxidation of the high aspect ratio structures, loading the substrate into a chamber body in the presence of nitrogen.
• In one or more embodiment disclosed herein, the method further includes, before the initiating conformal radical oxidation of the high aspect ratio structures, initially heating the substrate.
• In one or more embodiment disclosed herein, the method further includes, while initially heating the substrate, exposing the substrate to at least one of oxygen, nitrogen, and a combination thereof.
• In one or more embodiment disclosed herein, the initially heating the substrate comprises operating a conductive heater at a temperature between 700° C. and 900° C. while the conductive heater is in contact with a substrate support.
• In one or more embodiment disclosed herein, the initially heating the substrate continues for at least 60 seconds.
• In one or more embodiment disclosed herein, the initially heating the substrate continues until a temperature of the substrate is at least 600° C.
• In one or more embodiment disclosed herein, after the initially heating the substrate, a temperature of the substrate is between 750° C. and 800° C.
• In one or more embodiment disclosed herein, heating the substrate comprises: conductively heating the substrate support to a temperature between about 700° C. and 900° C. with an electric resistance heating device.
• In one or more embodiment disclosed herein, the method further includes, while heating the substrate, exposing the substrate to oxygen or nitrogen.
• In one or more embodiment disclosed herein, the method further includes, while exposing the substrate to steam, heating the substrate.
• In one or more embodiment disclosed herein, the method further includes, while exposing the substrate to steam, maintaining a temperature of the substrate between 750° C. and 800° C.
• In one or more embodiment disclosed herein, the exposing the substrate to steam lasts between 5 seconds and 45 seconds.
• In one or more embodiment disclosed herein, the steam comprises at least 30% H2.
• In one or more embodiment disclosed herein, the exposing the substrate to steam comprises: generating steam with a steam source external to a processing chamber, wherein the substrate is contained in the processing chamber; and flowing the steam into the processing chamber.
• In one or more embodiment disclosed herein, the generating steam includes catalytic steam generation.
• In one or more embodiment disclosed herein, the flowing the steam includes providing a symmetrical distribution of steam around an axis of a substrate support in the processing chamber.
• In one or more embodiment disclosed herein, exposing the substrate to steam comprises mixing the steam with at least one of a carrier gas, oxygen, nitrogen, argon, an inert gas, and a combination thereof.
• In one or more embodiment disclosed herein, the method further includes, after the initiating conformal radical oxidation of the high aspect ratio structures, exposing the substrate to plasma.
• In one or more embodiment disclosed herein, the method further includes, after the initiating conformal radical oxidation of the high aspect ratio structures, and before the exposing the substrate to plasma, purging a chamber body containing the substrate.
• In one or more embodiment disclosed herein, after the exposing the substrate to plasma, a thickness of a silicon dioxide layer in a bottom region of the high aspect ratio structures is between 95% and 105% of a thickness of the silicon dioxide layer in a top region of the high aspect ratio structures.
• In one or more embodiment disclosed herein, after the exposing the substrate to plasma, a trench in the high aspect ratio structures remains unfilled.
• In one or more embodiment disclosed herein, the method further includes, while exposing the substrate to plasma, heating the substrate.
• In one or more embodiment disclosed herein, the method further includes forming the plasma from an oxygen-containing gas.
• In one or more embodiment disclosed herein, the oxygen-containing gas contains 5% to 10% hydrogen.
• In one or more embodiment disclosed herein, the high aspect ratio structures have an aspect ratio of at least 40:1.
• In one or more embodiment disclosed herein, the high aspect ratio structures comprise at least one of silicon nitride, crystalline silicon, or aluminum oxide.
• In one or more embodiment disclosed herein, the high aspect ratio structures comprise 3D NAND structures.
• In one or more embodiment disclosed herein, the substrate is disposed in a processing chamber; and the exposing the substrate to steam comprises: flowing the steam and a carrier gas into the processing chamber for a first duration; discontinuing the flow of steam while continuing the flow of the carrier gas for a second duration; and flowing the steam and the carrier gas into the processing chamber for a third duration.
• In one embodiment, a semiconductor device includes a silicon and nitrogen containing layer; a feature formed in the silicon and nitrogen containing layer having: a face substantially perpendicular to a substrate; a bottom region; a top region farther from the substrate than the bottom region; and an aspect ratio of at least 40:1; and an oxide layer on the face of the feature, the oxide layer having a thickness in the bottom region that is at least 95% of a thickness of the oxide layer in the top region.
• In one or more embodiment disclosed herein, the semiconductor device comprises at least one of a memory device, a 3D NAND flash memory device, a crystalline silicon, a strained silicon, a silicon germanium, a doped polysilicon, an undoped polysilicon, a doped silicon wafer, an undoped silicon wafer, a patterned wafer, a non-patterned wafer, a silicon on insulator, a carbon doped silicon oxides, a doped silicon, or combinations thereof.
• While the foregoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.

Claims (15)

1. A substrate oxidation assembly comprising:

a chamber body defining a processing volume;

a substrate support disposed in the processing volume;

a plasma source coupled to the processing volume;

a steam source fluidly coupled to the processing volume; and

a substrate heater capable of heating to between 700° C. and 1100° C.

2. The assembly ofclaim 1, further comprising a quartz-lined conduit fluidly coupling the steam source to the processing volume.

3. The assembly ofclaim 1, wherein the processing volume includes a plasma volume, the plasma source is coupled to the plasma volume, the steam source is coupled to an inlet of the chamber body, and the plasma volume is between the inlet and the substrate support.

4. The assembly ofclaim 1, further comprising a gas distributor coupled to the chamber body, wherein:

the gas distributor has one or more inlet ports,

the steam source is fluidly coupled to the one or more inlet ports, and

the gas distributor has one or more outlet ports facing the substrate support.

5. The assembly ofclaim 4, wherein:

the processing volume includes a plasma volume,

the plasma source is coupled to the plasma volume; and

the plasma volume is between the gas distributor and the substrate support.

6. The assembly ofclaim 1, wherein the plasma source includes at least one of a remote plasma source, magnetron typed plasma source, a Modified Magnetron Typed plasma source, a remote plasma oxygen source, a capcitively coupled plasma source, an inductively coupled plasma source, and a toroidal plasma source.

7. The assembly ofclaim 1, wherein the steam source includes at least one of an H₂O injector, an ultrapure H₂O injector, a catalytic steam generator, and a pyrogenic steam source.

8. The assembly ofclaim 1, further comprising at least one of a radiative heating source and a conductive heating source operatively coupled to the substrate support.

9. The assembly ofclaim 1, wherein the chamber is capable of conformal radical oxidation of high aspect ratio structures.

10. A method of processing a semiconductor substrate comprising:

initiating conformal radical oxidation of high aspect ratio structures of the substrate comprising:

conductively heating the substrate support to a temperature between about 700° C. and 900° C. with an electric resistance heating device; and

exposing the substrate to steam; and

conformally oxidizing the substrate.

11. The method ofclaim 10, further comprising, before the initiating conformal radical oxidation of the high aspect ratio structures, initially heating the substrate.

12. The method ofclaim 11, wherein the initially heating the substrate continues until a temperature of the substrate is at least 600° C.

13. The method ofclaim 10, further comprising, while exposing the substrate to steam, maintaining a temperature of the substrate between 750° C. and 800° C.

14. A semiconductor device, comprising:

a silicon and nitrogen containing layer;

a feature formed in the silicon and nitrogen containing layer having:

a face substantially perpendicular to a substrate;

a bottom region;

a top region farther from the substrate than the bottom region; and

an aspect ratio of at least 40:1; and

an oxide layer on the face of the feature, the oxide layer having a thickness in the bottom region that is at least 95% of a thickness of the oxide layer in the top region.

15. The semiconductor device ofclaim 14, wherein the semiconductor device comprises at least one of a memory device, a 3D NAND flash memory device, a crystalline silicon, a strained silicon, a silicon germanium, a doped polysilicon, an undoped polysilicon, a doped silicon wafer, an undoped silicon wafer, a patterned wafer, a non-patterned wafer, a silicon on insulator, a carbon doped silicon oxides, a doped silicon, or combinations thereof.

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