# Patent

## Title
Atomic layer deposition and conversion

## Abstract

A method for growing films for use in integrated circuits using atomic layer deposition and a subsequent converting step is described. In an embodiment, the subsequent converting step includes oxidizing a metal atomic layer to form a metal oxide layer. The atomic layer deposition and oxidation step are then repeated to produce a metal oxide layer having sufficient thickness for use as a metal oxide layer in an integrated circuit. The subsequent converting step, in an embodiment, includes converting the atomic deposition layer by exposing it to one of nitrogen to form a nitride layer, carbon to form a carbide layer, boron to form a boride layer, and fluorine to form a fluoride layer. Systems and devices for performing the method, semiconductor devices so produced, and machine readable media containing the method are also described.

## Background
This application is a Divisional of U.S. application Ser. No. 10/137,058, filed May 2, 2002 which is incorporated herein by reference.


FIELD OF THE INVENTION
The present invention relates to deposition techniques and, more particularly, to deposition techniques for forming thin films on wafers or substrates and then converting the films into a different another composition.
BACKGROUND OF THE INVENTION
Integrated circuits (IC) are often fabricated with one or more semiconductor devices, which may include diodes, capacitors, and different varieties of transistors. These devices are generally fabricated by creating thin films of various materials, e.g. metals, semiconductors or insulators, upon a substrate or semiconductor wafer. Wafer and substrate are used interchangeably to refer to semiconductor structures during processing, and may include other layers that have been fabricated thereon. The physical characteristics and tightly controlled placement of films on a substrate will define the performance of the semiconductor device and its surrounding circuitry. Many semiconductor devices require a dielectric layer that must be reliable. Specifically, the dielectric layer must be essentially free from defects that cause shorting through the dielectric layer. Oxides and nitrides are used to form dielectric layers in semiconductor devices.
One process for forming metal oxide thin films on semiconductor wafers is chemical vapor deposition (“CVD”). CVD is used to form a thin film of a desired material from a reaction of vapor-phase chemicals containing the chemical constituents of the material. CVD processes operate by confining one or more semiconductor wafers in a reaction chamber. The chamber is filled with one or more gases that surround the wafer. The gases for the deposition of metal oxides includes a metal precursor and a reactant gas, e.g. water vapor, to be introduced into the chamber at the same time. Energy is supplied within the chamber and particularly to the reactant gases near the wafer surface. A typical energy is heat applied to the substrate. The energy activates the reactant gas chemistry to deposit a film from the gases onto the heated substrate. Such chemical vapor deposition of a solid onto a surface involves a heterogeneous surface reaction of the gaseous species that adsorb onto the surface. The rate of film growth and the quality of the film depend on the process conditions. Unfortunately, the metal precursor and the reactant gas also react during the gas phase remote from the substrate. Such a gas phase reaction produces contaminants and/or involve a significant quantity of precursor so that an insufficient amount is available for deposition on the substrate. As a result, the gas phase reaction may become dominant and the thin film coverage is poor. That is, pinholes may be formed in the resulting metal oxide layer. Moreover, using water (H2O) gas as the reactant gas results in impurities, such as hydroxide (OH), remaining in the resulting metal oxide layer.
Semiconductor fabrication continues to advance, requiring finer dimensional tolerances and control. Modem integrated circuit design has advanced to the point where line width may be 0.25 microns or less. As a result, repeatability and uniformity of processes and their results is becoming increasingly important. Generally, it is desired to have thin films deposited on the wafer to save space. Yet reducing the thickness of films can result in pinholes and in less mechanical strength.
Another development in the field of thin film technology for coating substrates is atomic layer deposition (ALD). A description of ALD is set forth in U.S. Pat. No. 5,879,459, which is herein incorporated by reference in its entirety. ALD operates by confining a wafer in a reaction chamber at a typical temperature of less than 300 degrees C. Precursor gas is pulsed into the chamber, wherein the pulsed precursor forms a monolayer on the substrate by chemisorption. The low temperature limits the bonding of the precursor to chemisorption, thus only a single layer, usually only one atom or molecule thick, is grown on the wafer. Each pulse is separated by a purge pulse which completely purges all of the precursor gas from the chamber before the next pulse of precursor gas begins. Each injection of precursor gas provides a new single atomic layer on the previously deposited layers to form a layer of film. Obviously, this significantly increases the time it takes to depose a layer having adequate thickness on the substrate. As a numerical example, ALD has a typical deposition rate of about 100 Å/min and CVD has a typical deposition rate of about 1000 Å/min. For at least this reason, ALD has not met with widespread commercial acceptance.
In light of the foregoing, there is a need for fabrication of thin films which are thinner and have a reduced number of defects.
SUMMARY OF THE INVENTION
The above mentioned problems with thin film fabrication techniques are addressed by the present invention and will be understood by reading and studying the following specification. Systems and methods are provided for fabricating thin films on substrates. The fabrication technique of the present invention grows a thin film by atomic layer deposition and then converts the film to produce a thin film having a different composition than the ALD deposited film. In an embodiment, each ALD thin film is converted before a subsequent ALD film is deposited. In one embodiment of the invention, a metal film is deposited by ALD. The metal film is then oxidized to produce a metal oxide film. In an embodiment, the metal is aluminum. In an embodiment, the metal is titanium. In an embodiment, the metal is tantalum.
In an embodiment, the thin film formed by atomic layer deposition is converted from an essentially pure metal film to a compound film that includes the metal and at least one second element. In an embodiment, the second element is oxygen. In an embodiment, the compound film is an oxide. In an embodiment, the second element is nitrogen. In an embodiment, the compound film is a nitride. In an embodiment, the second element is boron. In an embodiment, the compound film is a boride. In an embodiment, the second element is carbon. In an embodiment, the compound film is a carbide. In an embodiment, the second element is fluorine. In an embodiment, the compound film is a fluoride.
In an embodiment, a laminate or compound layer having at least two compounds in the layer is formed. The first element layer is deposited by ALD. This layer is then converted to a compound. A second element layer is deposited by ALD. This layer is then converted to a compound. In an embodiment, both the first and second elements are deposited by ALD and then both elements are converted. In an embodiment, one of the first element layer and second element layer is deposited by ALD and not converted. If the one layer includes a compound, then it is deposited by ALD in its compound form. The other of the first element layer and the second element layer is converted.
Additional embodiments of the invention include deposition devices and systems for forming metal oxide films on substrates, and machine readable media having fabrication instructions stored thereon, all according to the teachings of the present invention as described herein.
These and other embodiments, aspects, advantages, and features of the present invention will be set forth in part in the description which follows, and in part will become apparent to those skilled in the art by reference to the following description of the invention and referenced drawings or by practice of the invention. The aspects, advantages, and features of the invention are realized and attained by means of the instrumentalities, procedures, and combinations particularly pointed out in the appended claims.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a flow chart of the deposition process of an embodiment of the invention.
FIG. 2A is a flowchart of the deposition process of an embodiment of the invention.
FIG. 2B is a time graph of a deposition process of the present invention.
FIG. 3 is a view of a thin film of the present invention as a dielectric layer in a capacitor and as a gate layer in a transistor.
FIG. 4 is a view of a reactor for use with the process of the present invention.
FIG. 5 is a view of a reactor system for use with the process of the present invention.
FIG. 6 is a view of a memory system containing a semiconductor device having a thin film according to the present invention.
FIG. 7 is a view of a wafer containing semiconductor dies, each having a semiconductor device with a thin film of the present invention.
FIG. 8 is a block diagram of a circuit module that has a semiconductor device with a thin film of the present invention.
FIG. 9 is a block diagram of a memory module that has a semiconductor device with a thin film of the present invention.
FIG. 10 is a block diagram of an electronic system that has a semiconductor device with a thin film of the present invention.
FIG. 11 is a block diagram of a memory system that has a semiconductor device with a thin film of the present invention.
FIG. 12 is a block diagram of a computer system that has a semiconductor device with a thin film of the present invention.



DESCRIPTION OF THE EMBODIMENTS
In the following detailed description of the invention, reference is made to the accompanying drawings which form a part hereof, and in which is shown, by way of illustration, specific embodiments in which the invention may be practiced. These embodiments are described in sufficient detail to enable those skilled in the art to practice the invention. Other embodiments may be utilized and structural, logical, and electrical changes may be made without departing from the scope of the present invention. The terms wafer and substrate used in the following description include any structure having an exposed surface onto which a layer is deposited according to the present invention, for example to form the integrated circuit (IC) structure. The term substrate is understood to include semiconductor wafers. The term substrate is also used to refer to semiconductor structures during processing, and may include other layers that have been fabricated thereupon. Both wafer and substrate include doped and undoped semiconductors, epitaxial semiconductor layers supported by a base semiconductor or insulator, as well as other semiconductor structures well known to one skilled in the art. The term conductor is understood to include semiconductors, and the term insulator is defined to include any material that is less electrically conductive than the materials referred to as conductors. The following detailed description is, therefore, not to be taken in a limiting sense, and the scope of the present invention is defined only by the appended claims, along with the full scope of equivalents to which such claims are entitled.
According to the teachings of the present invention, fabrication of films on substrates, devices and systems for such fabrication, media containing instructions therefor, and integrated circuits produced according to the present invention are described.
The use, construction and fundamental operation of reactors for deposition of films are understood by those of ordinary skill in the art of semiconductor fabrication. The present invention may be practiced on a variety of such reactors without undue experimentation. Furthermore, one of ordinary skill in the art will comprehend the necessary detection, measurement, and control techniques in the art of semiconductor fabrication as well as the more inclusive art of industrial processing for producing films on substrates upon reading the disclosure.
It will be understood that the terms “precursor” and “reactant” are used herein to differentiate between a chemical compound that includes a metal component to be deposited on a substrate and a gas which reacts with the compound to deposit the metal component on a wafer. This nomenclature is used herein as a tool to clearly describe the invention as both the “precursor” and the “reactant” chemically react with each other to form the desired film on the substrate. Accordingly, the term “precursor” is not intended to imply a time relationship with the “reactant” unless explicitly described.
Applicant hereby incorporates by reference copending U.S. patent application Ser. No. 09/782,207, which is assigned to the assignee of the present application.
FIG. 1 depicts an atomic layer deposition (ALD) process according to the teachings of the present invention. A substrate is prepared to receive a compound layer, step 15. This includes forming required layers, trenches, oxides such as field oxides and other structures on the base surface of a wafer. In an embodiment, the compound layer is a metal nitride. In an embodiment, the compound layer is a carbide. In an embodiment, the compound layer is a boride. In an embodiment, the compound layer is a fluoride. When depositing a dielectric layer for a capacitor, a field insulator is formed on the wafer. The field insulator is etched to form a trench. A bottom electrode layer is deposited in the trench. Thereafter, the dielectric layer, e.g., metal oxide or metal nitride, is deposited on the bottom electrode layer according to the teachings of the present invention. After the dielectric is formed a top electrode layer is deposited on the dielectric layer. The remaining structure for the integrated circuit is then formed. When depositing a gate oxide for a transistor, the source and drain are formed in the substrate. A gate insulator, e.g., metal oxide, layer is formed on the substrate intermediate the source and drain according to the teachings of the present invention. Thereafter, the gate is formed on the gate insulator. The remaining structure for the integrated circuit is then formed. Step 17 is the first step in the ALD process. A first gas flows into a reaction chamber containing the substrate. The first gas is deposited at the surface of the substrate. The first gas includes a first element that forms part of the desired compound. In an embodiment, the first gas includes titanium. In an embodiment, the titanium is a TiCl4 gas. In an embodiment, the first gas includes tantalum. In an embodiment, the tantalum is a TaCl5 gas. In an embodiment, the first gas includes aluminum. In an embodiment, the aluminum is a trimethylaluminum (TMA) gas. A second gas flows into the chamber containing the substrate and first gas, step 19. The second gas is deposited at the surface of the substrate. The second gas includes a reactant element that will react with the first gas to deposit a first-element containing layer on the substrate. In an embodiment, the second gas is activated hydrogen. In an embodiment, the second gas is not H2O. The first and second gases are reacted in an ALD reaction to form a monolayer of metal film, step 21, in an embodiment. In this embodiment of ALD, the monolayer of metal film formed by the first and second gases is only about one molecule in thickness. The monolayer is an essentially pure layer of the first element. Essentially pure is defined as greater than 99% pure. In a more desirable embodiment, essentially pure is greater than 99.9% pure, plus or minus about 0.1%. In an even more desirable embodiment, essentially pure is greater than 99.99% pure, plus or minus 0.01%. In another embodiment of ALD, the first and second gases react to form a layer that is greater than a monolayer. After the ALD layer is formed on the substrate, the ALD layer is exposed to a reacting gas, step 23. The reacting gas converts the ALD layer containing the first element into a compound containing the first element and at least a second element from the reacting gas. In an embodiment, the reacting gas includes oxygen. In an embodiment, the oxidizing gas is dioxide (O2). In an embodiment, the oxidizing gas is ozone (O3). In an embodiment, the oxidizing gas is nitrogen oxide (N2O). In an embodiment, the oxidizing gas is activated oxide (O*). When the metal monolayer is titanium, then the oxidizing gas converts the titanium monolayer to ATiO3, where A denotes Ba or Sr or both. When the metal monolayer is tantalum, then the oxidizing gas converts the tantalum monolayer to Ta2O5. When the metal monolayer is aluminum, then the oxidizing gas converts the aluminum monolayer to lumina (Al2O3). The process is repeated, step 25, until the desired thickness of the final layer of the first and second elements is formed. The process returns to step 17 to begin forming another ALD layer or monolayer of a first element, which is then converted, according to the teachings of the present invention. In an embodiment, the first element is a metal and the second element is oxygen. After the final layer has the desired thickness, then additional integrated circuit fabrication processes are performed on the substrate as needed, step 27.
FIG. 1 also shows an embodiment of the present invention in broken line. Steps 15, 17, 19 and 21 are the same as described above. This embodiment repeats the ALD steps 17, 19, 21 until the ALD layer has the final, desired thickness, step 31. Thereafter, the ALD deposited layer is converted, step 33. In an embodiment, converting includes reacting the ALD layer with at least one second element to transform the ALD layer (single element layer) into a compound layer (multiple element layer). In an embodiment, reacting is oxidizing. In an embodiment, the first element is a metal. The process then proceeds, if needed, to step 27.
FIG. 2A shows an ALD process 200 according to the teachings of the present invention. ALD process 200, in the illustrated embodiment, begins by initiating an inert purge gas flow through a reactor (210). The purge gas maintains the chamber at a generally constant pressure. In one embodiment of the present invention the purge gas flow is pulsed, for example only injecting purge gas between other gas pulses. In another embodiment, purge gas is not used at all, i.e. step 210 is not performed.
The precursor gas containing a first element, e.g., metal, to be deposited on the substrate now flows into the reaction chamber (212). The metals include, for example, titanium, tantalum, or aluminum. The metals can also include alloys of these metals or other metal that one of ordinary skill would deposit on a substrate. The precursor gas flow continues until a volume closely adjacent the surface of the substrate on which the metal will be deposited is saturated by the precursor gas (214). According to the teachings of the present invention, the precursor gas saturates the topology of the substrate so that adequate precursor material is adjacent the substrate surface by the precursor gas entering and filling the steps, trenches, and holes. One of ordinary skill will understand the same upon reading the disclosure. The precursor gas flow, as well as purge gas flow if present, continues until the required saturation occurs depending on the processing conditions dictated by the type of substrate and precursor gas, and the topology of the substrate (216). A substrate having numerous or high aspect steps may require a longer precursor gas flow period than a substrate which has few steps or relative low aspect steps
Precursor gas flow ends once the precursor gas saturates adjacent the substrate according to the processing conditions of the present deposition (218). After or substantially at the same time precursor gas flow is stopped, reactant gas flow (for example, activated hydrogen) begins in the reaction chamber (220). Reactant gas continues to flow into the reaction chamber until the reactant gas saturates the volume adjacent the surface of the substrate on which the substance in the precursor gas will be deposited (222). The precursor gas and the reactant gas chemically react and deposit the desired material in a ALD layer, e.g., monolayer, on the substrate. In an embodiment, the deposited monolayer is about one atomic layer thick. In an embodiment, the deposited ALD layer is more than one atomic layer thick. The monolayer and the ALD layer are an essentially pure layer of a single element.
The present process may continue the purge gas flow while the reactant gas flows into the reaction chamber (224). Once a sufficient quantity of reaction gas is present to complete the reaction with the precursor to deposit a layer on the substrate, reaction gas flow ends (226). Purge gas flow may continue to partially flush the residual reaction and precursor gases and the by-product gas of the precursor and reactant reaction from the reaction chamber. A converting gas flows into the reaction chamber (228). The converting gas includes an oxidizing gas. The oxidizing gas oxidizes the monolayer, which is a metal, to form a dielectric layer. The oxidation continues until sufficient time has elapsed to oxidize essentially all of the metal monolayer (230). If the monolayer is not sufficiently oxidized the process continues flowing the oxidizing gas to the metal monolayer. Once the monolayer is sufficiently converted, e.g., oxidized, then the process proceeds to step 232. At step 232, it is determined if the converted layer formed by the previous steps has the desired film thickness. If the converted formed by one or a plurality of the ALD and conversion steps of the present invention has the desired thickness, then the ALD and conversion process of the present invention ends. If purge gas is still flowing, then the purge gas flow ends (234) usually after the remnants of the precursor, reactant, and by-product gases are purged from the chamber. The process of the present invention terminates at box 236. The reader should note that process termination may comprise initiation of further processing and does not necessarily require shutdown of the reactor, e.g. the above sequence of steps can be repeated or additional fabrication steps are performed. While one embodiment of the invention includes all of the above steps, the present invention includes other embodiments which do not include all of the above steps.
If the desired thickness of the layer has not been achieved (222), then the process returns to step 210 or step 212 and begins another cycle. The process then reiterates the above sequence/process until step 232 determines that the converted layer has the desired thickness.
One embodiment of the present inventive process is shown in FIG. 2B. The process begins with the flow of an inert purge gas and a precursor gas containing the first element into the reaction chamber. The precursor gas flows into the chamber until a sufficient quantity of the element that will form the monolayer is adjacent the substrate as determined by stoichiometry of the particular reaction needed to deposit the desired film on the substrate. The precursor must include a certain minimum amount of the first element to be deposited on a wafer and other reactive components that assist in the depositing the first element on the wafer. The precursor may flow into the reactor in a quantity greater than determined by the stoichiometry of the reaction. In this embodiment, the precursor gas flow ends followed by a short period of only purge gas flow. The reactant gas flows into the chamber until a sufficient quantity of reactant gas is available to react with the precursor at the surface of the substrate to deposit the desired first element film. An embodiment of the reactant gas include activated H. Like the precursor gas flow, the reactant gas and its flow reaches or exceeds the quantity that is determined by the stoichiometry of the particular reaction. Thereafter, the reactant gas flow stops. After the reactant gas flow stops, the converting gas flows into the reaction chamber. In an embodiment, the converting gas is an oxidizing gas and the first element monolayer is a metal. Accordingly, the metal monolayer on the substrate is oxidized. Thereafter, the flow of converting gas stops. This process is repeated until a converted film of a desired thickness is deposited on the substrate.
The converting gas includes an activated element that reacts with the ALD deposited layer. In an embodiment, the converting gas includes an activated oxygen. In an embodiment, the converting gas includes activated NH3. In an embodiment, the converting gas includes activated N2O.
The amounts of the precursor gas, the reactant gas, or the converting gas meets or exceeds the amount of material required by the stoichiometry of the particular reaction. That is, the amount of precursor, reactant, converting gas flow, in certain embodiments, provides excess mass in the reactor. The excess mass is provided to ensure an adequate reaction at the surface of the wafer. In this embodiment, the ratio of precursor, reactant, or converting components in the gas phase usually is different than the stoichiometry of the film.
FIG. 3 shows an integrated circuit 300 including a layer formed according to the teachings of the present invention. The layer is a dielectric in a capacitor 302. The layer is a gate insulator in a transistor 304. It is within the scope of the present invention to form the dielectric layer and gate insulator layer for both elements at the same time. It is within the scope of the present invention to form the dielectric layer for the capacitor and the gate insulator layer for the transistor at different times during fabrication. Capacitor 302 is formed on substrate 305. In an embodiment, a trench 307 is formed in insulator layer 309. A bottom electrode layer 311 is formed in the trench 307. A dielectric layer 313 is formed, according to the teachings of the present invention, on the bottom electrode layer 311. A top electrode layer 315 is formed on the dielectric layer 313. The transistor 304 is also formed on substrate 305. A field oxide 321 is formed on the substrate 305. The source and drain regions 323 and 325 are doped into the substrate 305. A gate insulator, e.g. an oxide or a nitride, layer 327 is formed according to the teachings of the present invention on the substrate 305 intermediate the source and drain regions 323 and 325. A gate 329 is formed on the gate insulator layer 327.
Dielectric layer or gate insulator layer 313 or 327 is a metal oxide material having a composition that includes the form MOx. In one embodiment, the metal component M is a refractory metal. In an embodiment, the refractory metal is tantalum (Ta). In an embodiment, the refractory metal is titanium (Ti). In an embodiment, the refractory metal is tungsten (W). The refractory metals of chromium (Cr), cobalt (Co), hafnium (Hf), molybdenum (Mo), niobium (Nb), vanadium (V) and zirconium (Zr) are included in some embodiments. Benefits may be derived by matching the metal oxide layer to the adjacent metal-containing electrode. For example, the TaOx layer 313 or 327 can be grown on a tantalum containing bottom electrode layer.
FIG. 4 depicts one embodiment of an atomic layer deposition (ALD) reactor 400 suitable for practicing the present invention. FIG. 4 is provided for illustrative purposes and the invention may be practiced with other reactors. The embodiment shown in FIG. 4 includes a chamber 401 that is a pressure-sealed compartment for mounting a substrate 402 on susceptor 407. Chamber 401 is typically manufactured from aluminum and is designed to contain a low-pressure environment around substrate 402 as well as to contain process gases, exhaust gases, and heat or plasma energy within chamber 401. The illustrated substrate 402 includes a substrate base 402A on which are deposited first and second layers 402B and 402C. Inlet gas manifold 403 supplies process gases, for example precursor gases, reactant gases and converting gases, at a controlled flow rates to substrate 402. A source of precursor gas 416 is connected to manifold 403. A source of purge gas 417 is connected to manifold 403. A source of reactant gas 418 is also connected to manifold 403. A source of converting gas 419 is also connected to manifold 403. Carrier gases, such as helium, argon or nitrogen, may also be supplied in conjunction with the gases supplied by the manifold as is known and understood by one of ordinary skill in the art. Chamber 401 also incorporates a pumping system (not shown) for exhausting spent gases from chamber 401 through exhaust port 404.
ALD reactor 400 includes means for supplying energy to the reactable constituents or compounds in the process gases in chamber 401 on the surface of the substrate 402. The supplied energy causes the reactable constituents to react or decompose and deposit a thin film onto an upper surface of substrate 402. In one embodiment, the supplied energy includes thermal energy supplied by heat lamps 406. In the illustrated example, lamps 406 are positioned in the base of chamber 401. Heat lamps 406 emit a significant amount of near-infra red radiation that passes through susceptor 407 to heat substrate 402. Alternatively, susceptor 407 is heated by heat lamps 406 and substrate 402 is heated by conduction from susceptor 407. The heat lamps 406 may be placed at alternate locations according to the parameters of the specific deposition process being performed according to the present invention.
Another embodiment supplies reaction energy by a radio frequency (RF) generator 408 as shown in FIG. 4. RF generator 408 creates a RF field between substrate 402 and an anode. In the embodiment shown in FIG. 4, susceptor 407 is grounded while the RF signal is applied to a process gas manifold 409. Alternative and equivalent ALD reactor designs will be understood by reading the disclosure. An RF anode may be provided separately (not shown) and process gas manifold 409 may be electrically isolated from the RF supply. For example, the RF signal is applied to susceptor 407 and process gas manifold 409 is grounded.
In general, the energy sources 406 and 408 are intended to provide sufficient reaction energy in a region near the surface of substrate 402 to cause decomposition and/or reaction of the constituents of the present gas to deposit the first element, e.g., the metal species, in the process gases onto a surface of the substrate. One of ordinary skill in the art will understand upon reading the disclosure that any one, combination, or equivalent of the above can be employed to provide the necessary reaction energy.
One embodiment includes plasma reactors because these allow film deposition at lower temperatures and are used in the semiconductor industry. However, some reactant constituents in the process gases may deposit at low temperatures using only thermal energy or other energy sources. Hence, the invention encompasses reactor designs using any energy source including either thermal heating, RF plasma, or the like.
ALD reactor 400 is illustrated as a single wafer reactor, but it should be understood that the invention is applicable to batch reactors.
Furthermore, ALD reactor 400 includes associated control apparatus (not shown) for detecting, measuring and controlling process conditions within ALD reactor 400. Associated control apparatus include, as examples, temperature sensors, pressure transducers, flow meters and control valves. Associated control apparatus further include other devices suitable for the detection, measurement and control of the various process conditions described herein.
One of ordinary skill in the art will comprehend other suitable reactors for practicing the invention described in this application, for example the reactors described in U.S. Pat. Nos. 5,879,459 and 6,305,314, herein incorporated by reference.
FIG. 5 represents an ALD system 500 suitable for practicing the invention. ALD system 500 contains the ALD reactor 400 and a control system 510. ALD reactor 400 and control system 510 are in communication such that process information is passed from ALD reactor 400 to control system 510 through communication line 520, and process control information is passed from control system 510 to ALD reactor 400 through communication line 530. It is noted that communication lines 520 and 530 may represent only one physical line, in which communications are bidirectional.
The control system 510 includes, integrally or separable therefrom, a machine readable media 535 which contains instructions for performing the present invention. Media 535 may be an electrical, magnetic, optical, mechanical, etc. storage device that stores instructions that are read by control system 510. Such storage devices include magnetic disks and tape, optical disks, computer memory, etc. Control system 510 may also include a processor (not shown) for issuing instructions to control reactor 400 based upon instructions read from machine readable media 535.
Memory Devices
FIG. 6 is a simplified block diagram of a memory device 600 according to one embodiment of the invention. The memory device 600 includes an array of memory cells 602, address decoder 604, row access circuitry 606, column access circuitry 608, control circuitry 610, and Input/Output circuit 612. The memory is operably coupled to an external microprocessor 614, or memory controller for memory accessing. The memory device 600 receives control signals from the processor 614, such as WE*, RAS* and CAS* signals. The memory device 600 stores data which is accessed via I/O lines. It will be appreciated by those skilled in the art that additional circuitry and control signals can be provided, and that the memory device of FIG. 6 has been simplified to help focus on the invention. At least one of the memory cells or associated circuitry has an integrated circuit structure or element in accordance with the present invention, e.g., a metal oxide layer formed according to the present invention.
It will be understood that the above description of a memory device is intended to provide a general understanding of the memory and is not a complete description of all the elements and features of a specific type of memory, such as DRAM (Dynamic Random Access Memory). Further, the invention is equally applicable to any size and type of memory circuit and is not intended to be limited to the DRAM described above. Other alternative types of devices include SRAM (Static Random Access Memory) or Flash memories. Additionally, the DRAM could be a synchronous DRAM commonly referred to as SGRAM (Synchronous Graphics Random Access Memory), SDRAM (Synchronous Dynamic Random Access Memory), SDRAM II, and DDR SDRAM (Double Data Rate SDRAM), as well as Synchlink or Rambus DRAMs and other emerging DRAM technologies.
Semiconductor Dies
With reference to FIG. 7, for one embodiment, a semiconductor die 710 is produced from a wafer 700. A die 710 is an individual pattern, typically rectangular, on a substrate or wafer 700 that contains circuitry, or integrated circuit devices, to perform a specific function. A semiconductor wafer 700 will typically contain a repeated pattern of such dies 710 containing the same functionality. Die 710 contains circuitry for the inventive memory device, as discussed above. Die 710 may further contain additional circuitry to extend to such complex devices as a monolithic processor with multiple functionality. Die 710 is typically packaged in a protective casing (not shown) with leads extending therefrom (not shown) providing access to the circuitry of the die for unilateral or bilateral communication and control. Each die 710 includes at least one ALD deposited and converted layer, e.g., a metal oxide, according to the present invention.
Circuit Modules
As shown in FIG. 8, two or more dies 710 may be combined, with or without protective casing, into a circuit module 800 to enhance or extend the functionality of an individual die 710. Circuit module 800 may be a combination of dies 710 representing a variety of functions, or a combination of dies 710 containing the same functionality. One or more dies 710 of circuit module 800 contain at least one ALD deposited and converted layer, e.g., a metal oxide, in accordance with the present invention.
Some examples of a circuit module include memory modules, device drivers, power modules, communication modems, processor modules and application-specific modules, and may include multilayer, multichip modules. Circuit module 800 may be a subcomponent of a variety of electronic systems, such as a clock, a television, a cell phone, a personal computer, an automobile, an industrial control system, an aircraft and others. Circuit module 800 will have a variety of leads 810 extending therefrom and coupled to the dies 710 providing unilateral or bilateral communication and control.
FIG. 9 shows one embodiment of a circuit module as memory module 900. Memory module 900 contains multiple memory devices 910 contained on support 915, the number generally depending upon the desired bus width and the desire for parity. Memory module 900 accepts a command signal from an external controller (not shown) on a command link 920 and provides for data input and data output on data links 930. The command link 920 and data links 930 are connected to leads 940 extending from the support 915. Leads 940 are shown for conceptual purposes and are not limited to the positions shown in FIG. 9. At least one of the memory devices 910 contains a ALD deposited and converted layer, e.g., a metal oxide, according to the present invention.
Electronic Systems
FIG. 10 shows one embodiment of an electronic system 1000 containing one or more circuit modules 800. Electronic system 1000 generally contains a user interface 1010. User interface 1010 provides a user of the electronic system 1000 with some form of control or observation of the results of the electronic system 1000. Some examples of user interface 1010 include the keyboard, pointing device, monitor or printer of a personal computer; the tuning dial, display or speakers of a radio; the ignition switch, gauges or gas pedal of an automobile; and the card reader, keypad, display or currency dispenser of an automated teller machine, or other human-machine interfaces. User interface 1010 may further describe access ports provided to electronic system 1000. Access ports are used to connect an electronic system to the more tangible user interface components previously exemplified. One or more of the circuit modules 800 may be a processor providing some form of manipulation, control or direction of inputs from or outputs to user interface 1010, or of other information either preprogrammed into, or otherwise provided to, electronic system 1000. As will be apparent from the lists of examples previously given, electronic system 1000 will often be associated with certain mechanical components (not shown) in addition to circuit modules 800 and user interface 1010. It will be appreciated that the one or more circuit modules 800 in electronic system 1000 can be replaced by a single integrated circuit. Furthermore, electronic system 1000 may be a subcomponent of a larger electronic system. It will also be appreciated that at least one of the memory modules 800 contains a ALD deposited and converted layer, e.g., a metal oxide, according to the present invention.
FIG. 11 shows one embodiment of an electronic system as memory system 1100. Memory system 1100 contains one or more memory modules 900 and a memory controller 1110. The memory modules 900 each contain one or more memory devices 910. At least one of memory devices 910 contain ALD deposited and converted layer, e.g., a metal oxide, according to the present invention. Memory controller 1110 provides and controls a bidirectional interface between memory system 1100 and an external system bus 1120. Memory system 1100 accepts a command signal from the external bus 1120 and relays it to the one or more memory modules 900 on a command link 1130. Memory system 1100 provides for data input and data output between the one or more memory modules 900 and external system bus 1120 on data links 1140.
FIG. 12 shows a further embodiment of an electronic system as a computer system 1200. Computer system 1200 contains a processor 1210 and a memory system 1100 housed in a computer unit 1205. Computer system 1200 is but one example of an electronic system containing another electronic system, i.e., memory system 900, as a subcomponent. Computer system 1200 optionally contains user interface components. Depicted in FIG. 12 are a keyboard 1220, a pointing device 1230, a monitor 1240, a printer 1250 and a bulk storage device 1260. It will be appreciated that other components are often associated with computer system 1200 such as modems, device driver cards, additional storage devices, etc. It will further be appreciated that the processor 1210 and memory system 1100 of computer system 1200 can be incorporated on a single integrated circuit. Such single package processing units reduce the communication time between the processor and the memory circuit. It will be appreciated that at least one of the processor 1210 and memory system 1100 contains a ALD deposited and converted layer, e.g., a metal oxide, according to the present invention.
While the above described embodiments describe first injecting the precursor gas and then injecting the reactant gas, it will be understood that it is within the scope of the present invention to first inject the reactant gas such that it saturates the volume adjacent the substrate and then inject the precursor. The precursor will enter the volume and react with the already present reactant gas and form a film on the substrate. The thus formed film is then converted according to the teachings of the present invention.
The above description described forming compounds, such as metal oxides, by ALD depositing a first monolayer, e.g., metal layer, on a substrate and/or a prior layer and then converting, e.g., oxidizing the metal layer to form a metal oxide. The present invention is also applicable to forming other elemental layers in an integrated circuit. For example, a layer is deposited using ALD and then the layer is nitrided. Thus, the layer is now a nitride layer. The process is repeated until the nitride layer has the desired thickness.
In another embodiment of the present invention, the layer is subjected to boron and thus becomes a boride layer. The above described steps are performed with the boron replacing the oxygen.
In another embodiment of the present invention, the layer is subjected to carbon and thus becomes a carbide layer. The above described steps are performed with the carbon replacing the oxygen.
In another embodiment of the present invention, the layer is subjected to fluorine and thus becomes a fluoride layer. The above described steps are performed with the fluorine replacing the oxygen.
In another embodiment of the present invention, the layer is subjected to phosphorus and thus becomes a phosphide layer. The above described steps are performed with the phosphorus replacing the oxygen.
The above description sets forth embodiments of the present invention that atomic layer deposit a single element, then subject it to a further element to convert the single element layer to an oxide, carbide, nitride, boride, fluoride, or phosphide two element layer. Embodiments of the present invention further provide for multiple element layer to be oxided or subjected to other elements for conversion as described herein. Accordingly, the present invention produces mixed phase films. In an embodiment, the mixed phase films include more than one base element. The first element is deposited using ALD in an ALD layer, monolayer or atomic layer. It is then converted according to the teachings of the present invention. A second element is deposited using ALD in a monolayer or atomic layer. The second element layer is then converted according to the teachings of the present invention. In an embodiment, the first or second element is an alloy of a metal. Consequently, mixed element film is formed by sequentially depositing and converting the first element and the subsequent element(s). It will be appreciated that the present method is adaptable to higher orders of elements in the film, wherein a third element is deposited and converted, . . . and an nth element is deposited and converted.
An example of such an ALD layer that is converted according to the teachings of the present invention include, but are not limited to, titanium and silicon in the base film. One embodiment would be formed by depositing both titanium and silicon by ALD then converting one or both according to the teachings of the present invention to form TiO2SiNx. Titanium is deposited in an ALD layer, such as a monolayer, using ALD and then converted according to the teachings herein. Silicon is deposited and then converted either before or after the titanium. Accordingly, the film that is formed alternates depositing and converting the titanium and the silicon.
An embodiment according to the teachings of the present invention includes depositing titanium and silicon by ALD and then converting both elements with oxygen to form TiOxSiOx. The titanium is first deposited, then oxidized. The silicon is then deposited, then converted using oxygen. In a further embodiment, the titanium and silicon are both deposited by ALD, then both converted by oxidizing the titanium and silicon. In a further embodiment, either the TiOx or SiOx is deposited according to ALD and the other of the TiOx or SiOx is deposited by ALD and then converted according to the teachings of the present invention.
An embodiment according to the teachings of the present invention includes depositing titanium by ALD and then converting the titanium using both oxygen and nitrogen to form a TiOxTiN layer. In a further embodiment, either the TiOx or TiN is deposited according to ALD and the other of the TiOx or TiN is deposited by ALD and then converted according to the teachings of the present invention.
An embodiment according to the teachings of the present invention includes depositing silicon by ALD and then converting the silicon using both oxygen and nitrogen to form a SiOxSiN layer. In a further embodiment, either the SiN or SiOx is deposited according to ALD and the other of the SiN or SiOx is deposited by ALD and then converted according to the teachings of the present invention.
An embodiment according to the teachings of the present invention includes depositing tantalum and silicon by ALD and converting tantalum with nitrogen to form TaNSi. The tantalum is deposited, then converted with nitrogen. The silicon is deposited by ALD. In a further embodiment, the present invention forms TaNTaSi.
An embodiment according to the teachings of the present invention includes depositing aluminum and titanium by ALD and then converting both elements with oxygen to form AlO3TiO2. The titanium is first deposited, then oxidized. The aluminum is then deposited, then converted using oxygen. In a further embodiment, the titanium and aluminum are both deposited by ALD, then both converted by oxidizing the titanium and aluminum. In a further embodiment, either the TiO2 or AlO3 is deposited according to ALD and the other of the TiO2 or AlO3 is deposited by ALD and then converted according to the teachings of the present invention.
The present invention includes methods of forming alloys or mixed element films and converting the alloy or mixed element films according to the teachings of the present invention. Some of the above embodiment describe specific elements that are deposited and converted or deposited in combination with elements that are converted according to the teachings of the present invention. It will be recognized that the order and methods described in conjunction with these specific elements are adaptable to other elements that are used to form layers in integrated circuits.
CONCLUSION
Thus, the present invention provides novel structures and methods for fabrication of thin films on substrates. The novel fabrication method of the present invention forms a first layer of a single element by ALD and then converts the first layer to a second layer having two constituent elements. The first layer is formed by atomic layer deposition and then converted. In an embodiment, each first layer produced during an atomic layer deposition is converted before a subsequent first layer is deposited on the prior converted sub-layer. In an embodiment, conversion is oxidation and the first layer is a metal. In an embodiment, each metal sub-layer produced during an atomic layer deposition is oxidized before a subsequent metal sub-layer is deposited on the prior oxidized metal sub-layer. Accordingly, each sub-layer is formed at a molecular level by atomic layer deposition and thus has a high quality. Quality includes low impurity and low defects. Each sub-layer is then oxidized. Accordingly, the oxidation is throughout the sub-layer and prevents non-oxidized areas in the sub-layer. The process is then repeated to until the oxidized sub-layers produce a film or layer that has the desired thickness.
The present invention includes any other applications in which the above structures and fabrication methods are used. The scope of the invention should be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled.

## Claims

1. A semiconductor device, comprising:
a substrate; and
an atomic layer deposition first layer deposited on the substrate, wherein the first layer is deposited by sequentially pulsing a precursor gas and a reactant into a reaction chamber, and wherein the precursor gas and reactant react to deposit the first layer on the substrate, the first layer including a material A, and wherein the first layer is converted to a second layer by a converting gas, the second layer including material B, and wherein the second layer forms a material Ax By, where x is the number of atomic bonds associated with the material A and y is the number of atomic bonds associated with the material B, and wherein the material B comprises at least one of carbon, boron and fluorine.

2. The semiconductor device according to claim 1, wherein the material A is an atomic layer deposition metal.

3. The semiconductor device according to claim 2, wherein the second layer is a dielectric.

4. The semiconductor device according to claim 3, wherein at least one of the first and the second metal layers include at least one of titanium, tantalum and aluminum.

5. The semiconductor device of claim 1, wherein the second layer comprises at least one of a carbide, a boride and a fluoride.

6. The semiconductor device of claim 4, wherein the second layer comprises at least one of carbide, a boride and a fluoride.

7. The semiconductor device of claim 1, wherein the second layer comprises carbon and boron, or carbon and fluoride, or boron and fluoride.

8. The semiconductor device of claim 3, wherein the second layer comprises a phosphide.

9. The semiconductor device of claim 4, wherein the second layer comprises a two element layer including a carbide, a nitride, a boride, a fluoride, or a phosphide.