SYSTEMS AND METHODS FOR PROCESSING THE SURFACE OF AN EPITAXIALLY GROWN SILICON FILM USING A RADICAL SPECIES
20230265582 · 2023-08-24
Inventors
Cpc classification
C30B25/186
CHEMISTRY; METALLURGY
International classification
Abstract
A method of processing a surface of an epitaxially grown silicon film includes using a radical species to remove random surface terminations from the surface of the epitaxially grown silicon film and to generate a substantially uniform distribution of surface terminations. Reaction systems for performing such a method, and epitaxially grown films prepared using such a method, also are provided.
Claims
1. A method of processing a surface of an epitaxially grown silicon film, the method comprising: using a first radical species to remove random surface terminations from the surface of the epitaxially grown silicon film and to generate a substantially uniform distribution of surface terminations.
2. The method of claim 1, wherein the first radical species reacts preferentially with the random surface terminations as compared to a bulk of the epitaxially grown silicon film.
3. The method of claim 1, wherein the first radical species comprises a hydrogen radical, and wherein the substantially uniform distribution of surface terminations comprises Si—H moieties.
4. The method of claim 1, wherein the first radical species comprises a chlorine radical, and wherein the substantially uniform distribution of surface terminations comprises Si—Cl moieties.
5. The method of claim 1, wherein the first radical species comprises a fluorine radical, and wherein the substantially uniform distribution of surface terminations comprises Si—F moieties.
6. The method of claim 1, wherein the first radical species comprises a nitrogen radical, and wherein the substantially uniform distribution of surface terminations comprises Si—N moieties.
7. The method of claim 1, wherein the random surface terminations comprise combinations of two or more of silicon moieties, hydrogen moieties, chlorine moieties, phosphorous moieties, and arsenic moieties.
8. The method of claim 1, wherein the first radical species forms covalent bonds with the surface.
9. The method of claim 1, further comprising using a second radical species to clean a wafer before forming the epitaxially grown silicon film on the wafer.
10. The method of claim 9, wherein the wafer is located within the same chamber during use of the second radical species to clean the wafer and during use of the radical species to remove the random surface terminations from the surface of the epitaxially grown silicon film.
11. A film deposition method, comprising: within a first chamber, using a first radical species to remove an oxide from a surface of a wafer; transferring the wafer to a second chamber; within the second chamber, epitaxially growing a silicon film on the surface from which the oxide was removed; transferring the wafer, having the epitaxially grown silicon film thereon, back to the first chamber; and within the first chamber, using a second radical species to remove random surface terminations from the surface of the epitaxially grown silicon film and to generate a substantially uniform distribution of surface terminations.
12. The method of claim 11, wherein the transferring operations are performed using robotics.
13. The method of claim 12, wherein the robotics transfer the wafer from the first chamber to the second chamber through a transfer chamber, and from the second chamber to the first chamber through the transfer chamber.
14. The method of claim 11, wherein the second radical species reacts preferentially with the random surface terminations as compared to a bulk of the epitaxially grown silicon film.
15. The method of claim 11, wherein the second radical species comprises a hydrogen radical, and wherein the substantially uniform distribution of surface terminations comprises Si—H moieties.
16. The method of claim 11, wherein the second radical species comprises a chlorine radical, and wherein the substantially uniform distribution of surface terminations comprises Si—Cl moieties.
17. The method of claim 11, wherein the second radical species comprises a fluorine radical, and wherein the substantially uniform distribution of surface terminations comprises Si—F moieties.
18. The method of claim 11, wherein the second radical species comprises a nitrogen radical, and wherein the substantially uniform distribution of surface terminations comprises Si—N moieties.
19. The method of claim 11, wherein the random surface terminations comprise combinations of two or more of silicon moieties, hydrogen moieties, chlorine moieties, phosphorous moieties, and arsenic moieties.
20. The method of claim 11, wherein the second radical species forms covalent bonds with the surface.
Description
BRIEF DESCRIPTION OF THE DRAWING FIGURES
[0038] While the specification concludes with claims particularly pointing out and distinctly claiming what are regarded as embodiments of the invention, the advantages of embodiments of the disclosure may be more readily ascertained from the description of certain examples of the embodiments of the disclosure when read in conjunction with the accompanying drawings, in which:
[0039]
[0040]
[0041]
[0042]
[0043]
[0044]
[0045] The illustrations presented herein are not meant to be actual views of any particular material, structure, or device, but are merely idealized representations that are used to describe embodiments of the disclosure.
DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS
[0046] Although certain embodiments and examples are disclosed below, it will be understood by those in the art that the invention extends beyond the specifically disclosed embodiments and/or uses of the invention and obvious modifications and equivalents thereof. Thus, it is intended that the scope of the invention disclosed should not be limited by the particular disclosed embodiments described below.
[0047] A number of example materials are given throughout the embodiments of the current disclosure, it should be noted that the chemical formulas given for each of the materials should not be construed as limiting and that the non-limiting example materials given should not be limited by a given example stoichiometry.
[0048] The terms “substantially,” “approximately,” and “about” used throughout this specification are used to describe and account for small fluctuations, such as due to variations in processing. For example, they may refer to less than or equal to ±10%, such as less than or equal to ±5%, such as less than or equal to ±2%, such as less than or equal to ±1%, such as less than or equal to ±0.5%, such as less than or equal to ±0.2%, such as less than or equal to ±0.1%, such as less than or equal to ±0.05%.
[0049] The term “silicon film” is intended to encompass films that include silicon, and that optionally may include one or more components other than silicon. For example, a “silicon film” may include silicon as well as a dopant, and optionally may consist essentially of the silicon and the dopant. Nonlimiting examples of dopants include phosphorous (P) and arsenic (As).
[0050] The surface of an epitaxially grown silicon film affects the electrical performance output of a device that includes such film. However, as recognized by the present inventor, the quality of such surface previously has not previously been well controlled. For example, after epitaxial growth of a silicon film is complete, the precursors are turned off and the reactor settings are changed, e.g., to appropriate wafer transfer conditions. As recognized by the present inventor, turning off inbound precursors leaves random surface terminations at the growth surface. For example, surface terminations include chemicals that are either partially or fully decomposed to a lower energy stage that is bound in some form to the film. Surface terminations may include, for example, fractions of the epitaxy precursors which are physisorbed or chemisorbed to the surface, or even hydrogenated silicon. Such surface terminations may be covalently bonded to the surface at random locations, resulting in random chemical identities of the surface. Such surface terminations may include, illustratively, Si-dopant moieties (which may be in their hydrogenated state) and/or higher energy Si—Cl moieties that are randomly mixed with lower energy Si—H moieties. Additionally, or alternatively, the random surface terminations may include different crystallographic orientations, such as a mixture of the higher energy silicon 100 and the lower energy silicon 111. Such a mixture of surface terminations on the film surface may detrimentally increase the film's propensity to oxidize. Additionally, or alternatively, such a mixture of surface terminations on the film surface may provide charge trap states that detrimentally and randomly affect the film's electrical characteristics in different regions.
[0051] It would be desirable to reduce or substantially eliminate the random terminations on the surface of an epitaxially grown silicon film, for example so as to reduce the film's propensity to oxidize and/or to reduce charge trap states. As recognized by the present inventor, reaction of the surface with radicals may be used to replace random surface terminations, such as Si-dopant and/or Si—Cl moieties, with a relatively uniform distribution of lower-energy surface terminations. The resulting surface may be more resistant to oxidation and/or formation of charge trap states than the random terminations, and thus may result in a surface with improved electrical qualities such as improved charge carrier mobility.
[0052] As provided herein, the surface of the epitaxially grown silicon may be processed using radical chemistry that otherwise has been used as a “preclean” step to remove oxide from the surface of a wafer before epitaxially growing a silicon film thereon. In one nonlimiting example, the surface of the epitaxially grown silicon film is hydrogenated using hydrogen radicals. Such radical-based hydrogenation may be performed at relatively low temperatures, e.g., about 200° C. or less, and may result in reduction or substantial removal of any surface terminations other than Si—H moieties as well as any higher-energy surfaces such as exposed silicon crystal planes. Accordingly, such radical-based hydrogenation may provide a relatively even distribution of Si—H moieties across a relatively low-energy silicon surface. Accordingly, it is expected that the film surface resulting from such processing may have a reduced number of defects and charge-trap states, may have a lower oxidation rate, and/or may have higher charge carrier mobility than a surface which has not been processed as such.
[0053] It is also expected that radical species besides hydrogen suitably may be used, and may provide a similarly low-energy surface including a relatively uniform distribution of surface terminations including the reaction products of such radicals and silicon atoms at the surface. For example, uniform hydrogen termination allows for improved robustness to oxidation and also does not degrade electrical performance. Alternatively, the halogen-based radicals F and Cl may be used similarly as hydrogen radicals to uniformly terminate the surface with halogen moieties (e.g., Si—Cl or Si—F). The resulting Si-halogen moieties may be dipoles in which electron density is drawn away from the silicon, and thus may be expected to shift the work function of the silicon film relative to a surface with uniform Si—H moieties. As another alternative, the nitrogen radical NH.sub.2 may be used to uniformly terminate the surface with nitrogen (Si—N) moieties. The resulting Si—N moieties may be dipoles in which electron density is drawn away from the nitrogen, and thus may be expected to shift the work function of the silicon film relative to a surface with uniform Si—H terminations and in a direction opposite that of the uniform Si-halogen terminations. In some examples, the surface terminations consist substantially of, or consist essentially of, the same type of moiety.
[0054] Note that attempting to hydrogenate the surface of the epitaxially grown silicon film using a baking procedure is not expected to be successful. For example, baking the epitaxially grown silicon film at temperatures exceeding 700° C. is expected to increase the likelihood that any dopant in the silicon film may undesirably precipitate or diffuse into undesired areas, such as a silicon channel disposed below or adjacent to the silicon film, degrading the device's electrical performance. Moreover, baking is prohibitive in some applications owing to the thermal budget specific to certain patterned wafers; where temperatures in excess of 700° C. would otherwise promote silicon reflow and ultimate reshaping of critical structures.
[0055]
[0056] At operation 101 illustrated in
[0057] As discussed above and in a manner such as illustrated in the inset of
[0058] As provided herein, a radical species may be used to remove such random surface terminations from the surface 130 of the epitaxially grown silicon film and to generate a substantially uniform distribution of surface terminations. For example, at operation 104 illustrated in
[0059] The second radical species R2 preferentially may react with the random surface terminations as compared to the bulk of the silicon film. For example, such random surface terminations may be of higher energy than the remainder of silicon film 120. Illustratively, silicon 100 is higher energy than silicon 111, and R2 therefore may react with the silicon 100 preferentially to the silicon 111. Etching higher energy surfaces is advantageous for ensuring the grown crystal adopts a self-limiting shape. A self-limiting crystal in epitaxy is one which has substantially only Si 111 planes at the surface. Moreover, etching higher energy surfaces may lead to less near surface defectivity. Accordingly, in some examples processed surface 131′ may consist essentially of a single crystallographic orientation (e.g., Si 111 and/or the same crystallographic orientation as silicon film 120) and may include a substantially uniform distribution of surface terminations. Surface 131′ may be substantially devoid of any random surface terminations.
[0060] In examples that include epitaxially growing silicon film 120, any suitable first radical species R1 may be used that substantially removes the oxide from wafer 110 during operation 100, and the first radical species may be generated in any suitable manner. In nonlimiting examples such as described with reference to
[0061] Additionally, in examples that include epitaxially growing silicon film 120, any suitable precursor(s) may be used that form such a film. For example, as described with reference to
[0062] Any suitable second radical species R2 may be used that removes random surface terminations from the surface of the epitaxially grown silicon film and generates a substantially uniform distribution of surface terminations, and the second radical species may be generated in any suitable manner. In some examples, the first and second radical species may be the same as one another. As such, the second radical species R2 may be generated using the same precursor and remote plasma unit as the first radical species R1. In other examples such as described with reference to
[0063] In some examples, first radical species R1 and/or second radical species R2 includes a fluorine, chlorine, nitrogen or hydrogen radical. In some examples, the fluorine radical may be generated using a nitrogen trifluoride (NF.sub.3) precursor which forms NF.sub.2 radical, or HF precursor which forms F radical. The chlorine radical may be generated using chlorine (Cl.sub.2) which forms Cl radical. The nitrogen radical may be generated using ammonia (NH.sub.3) which forms NH.sub.2 radical. The hydrogen radical may be generated using hydrogen (H.sub.2).
[0064] It will be appreciated that any suitable system(s) may be used to process the epitaxially grown silicon film using a radical species. In some examples, wafer 110 may be located within the same chamber during use of the first radical species R1 and during use of the second radical species R2. That is, wafer 110 need not necessarily be located in one chamber during use of first radical species R1 and located in a different chamber for use of second radical species R2. Instead, operations 100, 101, 104, and 105 described with reference to
[0065]
[0066] Controller 480 may be operably coupled to the first radical species precursor source unit 430, the second radical species precursor source unit 440, the inert gas source unit 450, and the remote plasma unit 420 (such electrical connections being illustrated in dash-dot lines). Controller 480 may be configured to control so as to implement operations 100, 101, 104, and 105 described with reference to
[0067] Controller 480 further may be configured to as to cause second radical species precursor source unit 440 to flow the second radical species precursor through gas line 460B and to cause the inert gas source unit to flow the inert gas through gas line 460C into remote plasma unit 420. Controller 480 also may be configured so as to cause the remote plasma unit 420 to ignite the resulting mixture of gases to form a plasma including second radical species R2, and to flow the second radical species through main gas line 470 to reaction chamber 410 so as to implement operation 104 described with reference to
[0068] Reaction chamber 410 may include stage 412 configured to hold wafer 410, and flow regulator 411 configured to provide for relatively even flow of gases to the surface of the wafer during operations 100, 101, 104, and 105.
[0069] It will be understood that components of system 400 described with reference to
[0070] Wafer starting chamber 510 may be configured to receive any suitable number of semiconductor wafers for processing. Controller 580 may be configured to cause robotics 520 to move wafer(s) from wafer starting chamber 510 to wafer transfer chamber 530. Controller 580 also may be configured to cause robotics 540 to move wafer(s) from wafer transfer chamber 530 to radicals subsystem 400 for processing such as described with reference to
[0071] It will be appreciated that systems 400 and 500 provide nonlimiting examples of hardware and software that may be used to process wafers in the manner provided herein. For example,
[0072] It will be appreciated that operation 650 suitably may be performed on any epitaxially grown silicon film, and that the film need not necessarily be grown within the context of method 600. That is, the epitaxially grown silicon film may be obtained from any suitable source, and operation 650 then performed thereon. In this regard, the use of the terms “first” and “second” are not intended to suggest that both such elements or operations need to be used.
[0073] Wafer 110, which may be used in operations 100-103 or 610-650 and in systems 400 or 500, may include any suitable combination of materials. For example, wafer 110 may consist essentially of a semiconductor wafer (such as a doped or undoped silicon wafer). Or, for example, wafer 110 may include a film that is disposed on a semiconductor wafer. Epitaxially grown silicon film 120 may be horizontally oriented (e.g., substantially parallel to the major surface of wafer 110), or may be vertically oriented (e.g., substantially perpendicular to the major surface of wafer 110). Wafer 110, epitaxially grown silicon film 120, and/or any other films that may be disposed on the wafer may be patterned.
[0074] For example, epitaxially grown silicon film 120 may include a component of a FINFET or a storage node capacitor for DRAM. In FINFET source/drain applications, there are particularly high standards for the quality of epitaxial silicon crystal growth on top of the fin structure. Even though a given process may produce good crystal quality, there often exist circumstances wherein the grown will proceed faster on one fin over another. This difference in growth rate may make it such that fins may grow together via the source/drain epitaxially grown silicon film. Alternatively, a situation may arise where one fin has little deposition, and another has superfluous deposition. Such growth rate differences may arise from random variation in the fin starting surfaces.
[0075] Etch back previously has been used to etch away higher energy surfaces from fins, leaving behind crystalline silicon. Etch backs can be tailored to be more or less aggressive, and can be used to tune the thickness profile locally. However, the chemicals used in etch back, such as HCl or Cl.sub.2, can have undesirably long lifetimes. Additionally, such chemicals may easily diffuse into the silicon film because their size is relatively small compared to the silicon crystal lattice. If an etchant moves into the silicon subsurface, then crystal quality of the subsurface may be negatively affected; for example, silicon may locally lose its diamond geometry by Si—Cl covalent bonding. Such bonding may negatively affect the electrical performance of the silicon film. Chemical etchants also may leach out dopants from epitaxially grown silicon films.
[0076] As provided herein, as an alternative to etching, radical species may be used to shape fins, e.g., by removing random surface terminations from the fins. Such radical species may not readily diffuse into the silicon crystal lattice, e.g., because they are too large and/or because they are so reactive that they react or recombine before substantial diffusion into the subsurface may occur. As such, the radical species substantially may not affect the crystal quality of the subsurface, nor leach out chemical etchants. Indeed, the radical species may improve the electrical performance of the silicon film by removing random surface terminations from the fins which otherwise may facilitate oxidation or provide charge trap sites in a manner such as described elsewhere herein.
[0077]
[0078] It will be appreciated that controller 480 may be implemented using any suitable combination of digital electronic circuitry, integrated circuitry, application specific integrated circuits (ASICs), field programmable gate arrays (FPGAs), central processing units (CPUs), graphical processing units (GPUs), computer hardware, firmware, software, and/or combinations thereof. For example, one or more functionalities of controller 480 may be implemented in one or more computer programs that are executable and/or interpretable on a programmable system including at least one programmable processor, which can be special or general purpose, coupled to receive data and instructions from, and to transmit data and instructions to, a storage system, at least one input device, and at least one output device. The programmable system or computing system can include clients and servers. A client and server are generally remote from each other and typically interact through a communication network. The relationship of client and server arises by virtue of computer programs running on the respective computers and having a client-server relationship to each other.
[0079] These computer programs, which can also be referred to as modules, programs, software, software applications, applications, components, or code, can include machine instructions for a programmable processor, and/or can be implemented in a high-level procedural language, an object-oriented programming language, a functional programming language, a logical programming language, and/or in assembly/machine language. As used herein, the terms “memory” and “computer-readable medium” refer to any computer program product, apparatus and/or device, such as magnetic discs, optical disks, solid-state storage devices, memory, and Programmable Logic Devices (PLDs), used to provide machine instructions and/or data to a programmable data processor, including a machine-readable medium that receives machine instructions as a computer-readable signal. The term “computer-readable signal” refers to any signal used to provide machine instructions and/or data to a programmable data processor. The computer-readable medium can store such machine instructions non-transitorily, such as would a non-transient solid-state memory or a magnetic hard drive or any equivalent storage medium. The computer-readable medium can alternatively or additionally store such machine instructions in a transient manner, such as for example as would a processor cache or other random access memory associated with one or more physical processor cores.
[0080] The computer components, software modules, functions, data stores and data structures can be connected directly or indirectly to each other in order to allow the flow of data needed for their operations. It is also noted that a module or processor includes but is not limited to a unit of code that performs a software operation, and can be implemented for example as a subroutine unit of code, or as a software function unit of code, or as an object (as in an object-oriented paradigm), or as an applet, or in a computer script language, or as another type of computer code. The software components and/or functionality can be located on a single computer or distributed across multiple computers and/or the cloud, depending upon the situation at hand.
[0081] In one nonlimiting example, controller 480 described with reference to
[0082] The example embodiments of the disclosure described above do not limit the scope of the invention, since these embodiments are merely examples of the embodiments of the invention, which is defined by the appended claims and their legal equivalents. Any equivalent embodiments are intended to be within the scope of this invention. Indeed, various modifications of the disclosure, in addition to those shown and described herein, such as alternative useful combination of the elements described, may become apparent to those skilled in the art from the description. Such modifications and embodiments are also intended to fall within the scope of the appended claims.