阅读说明：本技术 使用化学抑制对膜进行保形性调节 (Conformal modulation of films using chemical inhibition ) 是由 大卫·C·史密斯 丹尼斯·M·豪斯曼 于 2018-12-14 设计创作，主要内容包括：提供了在原子层沉积(ALD)中用于金属氧化物膜的保形性调节的方法和系统。一些示例性方法使用化学抑制。用于执行这种方法的示例系统包含：室；前体气体源；抑制前体气体源；具有相应的气流路径的一或更多注射器,其各自具有能连接至所述前体气体源或所述抑制前体气体源的入口,且适合于单独地或与另一注射器一起使前体气体在多个区域中的第一区域中以第一气体流率输送至所述室中以便以第一沉积速率形成第一膜,并且适合于在所述多个区域中的相同区域或第二区域中以第二气体流率输送抑制前体气体以抑制所述第一膜的生长。(Methods and systems for conformal tuning of metal oxide films in Atomic Layer Deposition (ALD) are provided. Some exemplary methods use chemical inhibition. An example system for performing such a method includes: a chamber; a precursor gas source; suppressing a precursor gas source; one or more injectors having respective gas flow paths, each having an inlet connectable to the precursor gas source or the inhibiting precursor gas source, and adapted to deliver, either alone or with another injector, precursor gas into the chamber at a first gas flow rate in a first zone of a plurality of zones to form a first film at a first deposition rate, and adapted to deliver inhibiting precursor gas at a second gas flow rate in the same zone or a second zone of the plurality of zones to inhibit growth of the first film.)

1. An Atomic Layer Deposition (ALD) apparatus, comprising:

a chamber;

a precursor gas source;

suppressing a precursor gas source;

one or more injectors having respective gas flow paths, each injector having an inlet connectable to the precursor gas source or the precursor gas suppressing source and being adapted to deliver precursor gas, either alone or with another injector, into the chamber at a first gas flow rate in a first zone of a plurality of zones to form a first film at a first deposition rate, and

adapted to deliver an inhibiting precursor gas at a second gas flow rate in the same or a second one of the plurality of zones to inhibit growth of the first film.

2. The ALD apparatus of claim 1, wherein the one or more injectors are further adapted to deliver the suppression precursor gas into the chamber prior to entry of the precursor gas into the chamber.

3. The ALD apparatus of claim 1, wherein the one or more injectors are further adapted to deliver the precursor gas into the chamber prior to entry of the suppression precursor gas into the chamber.

4. The ALD apparatus of claim 1, wherein the one or more injectors are further adapted to deliver the suppression precursor gas into the chamber while the precursor gas is admitted into the chamber.

5. The ALD apparatus of claim 1, wherein the one or more injectors are further adapted to deliver a second precursor gas at a third gas flow rate in one of the plurality of zones so as to form a second film at a second deposition rate.

6. The ALD apparatus of claim 5, wherein the one or more injectors are further adapted to deliver the second precursor gas while the suppression precursor gas is entering the chamber.

7. The ALD apparatus of claim 1, wherein the precursor gas includes a chelating agent.

8. The ALD apparatus of claim 1, wherein the chelating agent includes one or more of HAcAc, butane thiol, ethanol, and phosphine.

9. The ALD apparatus of claim 1, wherein the one or more injectors are further adapted to deliver a low exposure inhibiting precursor gas at an exposure level of less than 1% of a minimum exposure required to achieve saturation of the precursor gas on a planar surface.

10. A method for profile control in Atomic Layer Deposition (ALD), comprising:

flowing a precursor gas into a chamber of an ALD reactor at a first gas flow rate in a first zone of a plurality of zones in the chamber to form a first film at a first deposition rate; and

delivering an inhibiting precursor gas at a second gas flow rate in the same or a second region of the plurality of regions in the chamber to inhibit growth of the first film layer.

11. The method of claim 10, further comprising: delivering the suppression precursor gas into the chamber prior to entering the precursor gas into the chamber.

12. The method of claim 10, further comprising: delivering the precursor gas into the chamber prior to the suppressing precursor gas entering the chamber.

13. The method of claim 10, further comprising: delivering the suppression precursor gas into the chamber while the precursor gas is admitted into the chamber.

14. The method of claim 10, further comprising: delivering a second precursor gas in one of the plurality of zones at a third gas flow rate to form a second film in the chamber at a second deposition rate.

15. The method of claim 14, further comprising: delivering the second precursor gas while the suppressing precursor gas is entering the chamber.

16. The method of claim 10, further comprising: a chelating agent is included in the precursor gas.

17. The method of claim 16, further comprising: one or more of HAcAc, butanethiol, ethanol, and phosphine are included in the chelating agent.

18. The method of claim 10, further comprising: delivering the suppression precursor gas at an exposure level of less than 1% of a minimum exposure required to achieve saturation of the precursor gas on a planar surface.

Technical Field

The present invention relates generally to selective atomic layer deposition in semiconductor device fabrication, and more particularly to conformal tuning of metal oxide films using chemical inhibition. In one example, selective suppression is used to provide improved film profile control.

Background

Conventionally, Atomic Layer Deposition (ALD) is a thin film deposition technique used in a sequence based on gas phase chemical processes. ALD is considered a subclass of chemical vapor deposition. Most ALD reactions use two chemicals, commonly referred to as precursors. These precursors react with the surface of the material one at a time in a sequential, self-limiting manner. The thin film is deposited by repeated exposure to the separated precursors.

ALD is a critical process in semiconductor device and wafer fabrication and is part of a kit that can be used to synthesize nanomaterials. Profile control in metal oxide deposition can also be achieved using a periodic etch back step, but this introduces additional hardware and cost.

The present disclosure seeks to address at least these disadvantages. It should be noted that the information described in this section is presented to provide one of ordinary skill in the art with a background to the subject matter disclosed below and should not be considered prior art as being admitted.

Disclosure of Invention

In an exemplary embodiment, an ALD apparatus comprises: a chamber; a precursor gas source; suppressing a precursor gas source; one or more injectors having respective gas flow paths, each injector having an inlet connectable to the precursor gas source or the inhibiting precursor gas source and adapted to deliver, either alone or with another injector, precursor gas into the chamber at a first gas flow rate in a first zone of a plurality of zones to form a first film at a first deposition rate and to deliver inhibiting precursor gas at a second gas flow rate in the same zone or a second zone of the plurality of zones to inhibit growth of the first film.

In some examples, the one or more injectors are further adapted to deliver the suppression precursor gas into the chamber prior to entry of the precursor gas into the chamber. In some examples, the one or more injectors are further adapted to deliver the precursor gas into the chamber prior to the inhibiting precursor gas entering the chamber. In some examples, the one or more injectors are further adapted to deliver the suppression precursor gas into the chamber while the precursor gas is being admitted into the chamber. In some examples, the one or more injectors are further adapted to deliver a second precursor gas at a third gas flow rate in one of the plurality of zones to form a second film at a second deposition rate. In some examples, the one or more injectors are further adapted to deliver the second precursor gas while the suppression precursor gas is entering the chamber. The suppression precursor gas may comprise one or more of a chelating agent, a diketone, a thiol, an alcohol, and a phosphine. In some examples, the one or more injectors are further adapted to deliver a low exposure suppression precursor gas at an exposure level of less than 1% of the minimum exposure required to achieve saturation of the precursor gas on a flat surface.

Drawings

Some embodiments are shown by way of example, and not by way of limitation, in the figures of the accompanying drawings:

fig. 1A-1B are schematic cross-sectional views of a conformal structure, according to an exemplary embodiment.

Fig. 2A-2B contain schematic cross-sectional views of another conformal structure, according to an exemplary embodiment.

Fig. 3 contains a schematic cross-sectional view of a sub-conformal structure, according to an exemplary embodiment.

Fig. 4 contains a schematic cross-sectional view of a super-conformal structure, according to an exemplary embodiment.

Fig. 5 is a schematic diagram of an SMFD reactor in a respective dosing and purging mode, according to an exemplary embodiment.

Fig. 6 is a schematic diagram of an exemplary ICP plasma ALD reactor, according to an exemplary embodiment.

Fig. 7 is a schematic diagram of a remote plasma reactor, according to an exemplary embodiment.

Fig. 8 is a schematic diagram of a CCP plasma reactor, according to an exemplary embodiment.

Fig. 9 is a flowchart showing operations in a method according to an exemplary embodiment.

Fig. 10 is a flow chart showing operations in a method according to an exemplary embodiment.

FIG. 11 is a block diagram illustrating an example of a computer controller by which one or more example methods of the invention may be controlled.

Detailed Description

The following description includes systems, methods, techniques, instruction sequences, and computer program products that implement illustrative embodiments of the invention. In the following description, for purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of the exemplary embodiments. However, it should be clear to the skilled person that: the present invention may be practiced without these specific details.

Portions of the disclosure of this patent document contain material which is subject to copyright protection. The copyright owner has no objection to the facsimile reproduction by anyone of the patent document or the patent disclosure, as it appears in the patent and trademark office patent file or records, but otherwise reserves all copyright rights whatsoever. The following statements apply to any data in the accompanying drawings, which are described below and which form a part of this document: copy Lam Research Corporation, 2017-.

For various applications, Atomic Layer Deposition (ALD) has become an important technique for depositing thin films. Semiconductor processing is one of the major incentives for recent developments in ALD. International Technology Roadmapping for Semiconductors (ITRS) has used ALD for high dielectric constant gate oxides in MOSFET structures and copper diffusion barriers in back-end interconnects. Furthermore, ALD encounters challenging needs in other areas, including the deposition of high quality dielectrics to fabricate trench capacitors for DRAMs. Miniaturization in the semiconductor industry has resulted in a need for atomic-level control of thin film deposition. Miniaturization produces very high aspect ratio structures that need to be conformally coated. No other thin film technology approaches the conformality achieved by ALD on high aspect ratio structures. The need for continuous and pinhole-free films in semiconductor devices has prompted the development of ALD. Other applications outside the semiconductor industry with similar stringent requirements are: low electron leakage dielectrics for magnetic read/write heads and diffusion barrier coatings with low gas permeability.

As mentioned above, conventional ALD attempts to use sequential, self-limiting surface reactions to meet the needs of atomic layer control and conformal deposition. Most ALD processes are based on a binary reaction sequence, where two surface reactions occur and a binary compound film is deposited.

Today's ALD of metal oxides generally results in conformal (high exposure of both precursors) or sub-conformal (low exposure of both precursors) films. Cross-sectional views of exemplary conformal structures 100A and 100B are shown in fig. 1A-1B. In the various views, the ALD-produced overlayers 102 (fig. 1A) and 104 (fig. 1B) are "conformal" to the shape of the respective underlying structures 108 and 110. A further view of the conformal structure is provided in fig. 2. In the left view, the test structure 200 is shown. In the use of silicon dioxide (SiO)₂) Following ALD, a conformal layer 202 is formed over the structure 200, as shown in the right hand view.

On the other hand, a "sub-conformal" film is thicker near the top of the feature than at the bottom. An example of a sub-conformal film layer 300 is shown in fig. 3. High aspect ratio trenches can be seen at 302 in the underlying structure 304. The upper portion 305 of the membrane 300 is thicker in cross-section than the lower portion 306 of the membrane 300, the lower portion 306 being deeper in the trench 302.

For certain semiconductor applications, "super-conformal" films are desirable. The super-conformal film is thicker at the bottom of the feature than at the top. An example of a super-conformal film layer 400 is shown in fig. 4. Again, high aspect ratio trenches can be seen at 402 in the underlying structure 404. The upper portion 405 of the membrane 400 is thinner in cross-section than the lower portion 406 of the membrane 400, the lower portion 406 being deeper in the trench 402. The nanometer size of the sub-conformal and super-conformal structures is provided by the scales 308 and 408 visible in the lower right hand corner of the respective views.

Conventionally, the super-conformality in the features may be achieved by a controlled etch-back (etch-back) step, which is performed in a different module than that used for the deposition process, or using a plasma step, both of which add complexity and cost to the process.

In the present disclosure, alternative contour control methods are provided. An exemplary method in one aspect includes selectively suppressing feature tops. This can be achieved by: a low degree of exposure to an inhibiting precursor gas (also referred to herein as an inhibitor) is used so that the precursor adsorbs only to the top of the feature. The suppression precursor gas can be delivered in the same chamber as the deposition precursor and requires little (or no) additional hardware or tool modification. Suitable suppression precursors for metal oxide deposition may include chelating agents, diketones (e.g., acetylacetone (HAcAc)), thiols (e.g., butanethiol), alcohols (e.g., ethanol), and phosphines. Other inhibiting precursors are possible.

Inhibiting the exposure of the precursor may be expressed as a product of partial pressure and time. A reactive precursor such as trimethylaluminum may require about 10^-6Torr-second exposure to saturate the hydroxylated surface at 200 ℃. Thus, an example includes a 1 millisecond dose at a partial pressure of 1 millitorr (mtorr), or a 10 millisecond dose at a partial pressure of 0.1 mtorr. In the amine sealPrecursors with low reactivity on the end group surface, such as dichlorosilane, typically would require a 1 torr-second (torr sec) exposure at 400 ℃ to saturate the surface.

In some examples, the low degree of exposure to the suppression precursor gas may be defined as: an exposure level of less than 1% of the minimum exposure required to achieve precursor gas saturation on a flat surface. The following chart contains the approximate low exposure values in this regard.

Membrane system	Minimal exposure
		AlMe3+H2O Al2O3	10^-6torr sec
Hf(NMe2)4+H2O–>HfO2	10^-5torr sec
		SiH2(Net2)2+ O2 plasma SiO2	10^-4torr sec
SiH2Cl2+ NH3 plasma SiN	10^-1torr sec

Selective suppression may be used to provide improved film profile control. For example, using the affinity of a chelating agent (e.g., HAcAc) to adhere to and inhibit deposition on the metal oxide surface, deposition of a metal oxide film by ALD can be inhibited by exposing the substrate to the chelating agent in such a manner (e.g., using a low degree of exposure of the inhibitor) to limit adhesion to the fields and the top of the trench.

The methods of the present disclosure may be used, for example, in a remote plasma system or a capacitively coupled plasma system. A remote plasma system (also referred to as a downstream plasma system or an afterglow plasma system) is one in which plasma interaction with a material (e.g., a semiconductor wafer) occurs at a location remote from the plasma in the afterglow of the plasma.

A schematic diagram of an exemplary remote plasma system 700 is shown in fig. 7. The system includes a main processing chamber 702 and a remote plasma source 704. Also included within the system 700 is a gas source 714 and a vacuum pump 716. Plasma 706 passes through remote transport region 708 and gas baffle 710. Material interaction within the chamber occurs at a location 712 in the afterglow of the plasma, which is remote from the plasma source 704 or downstream of the plasma source 704.

Another example of a remote plasma system is shown in fig. 5. An ALD reactor for performing ALD with suppressed precursors is referred to herein as a simultaneous modulated flow and extractor (SMFD). A schematic diagram of such an SMFD reactor 500 is shown in fig. 5 in a corresponding dosing and purging mode. SMFD reactor 500 injects an inert flow gas at reactor inlet 502 during the purge mode and reactants enter the reactor at inlet 502 in the dosing mode. The inert gas exits the reactor 500 via the reactor outlet 504 during the dosing mode. Suppression precursors can be injected into the reactor during either stage, and the exposure can be controlled by adjusting the volume and rate of exchange gas. The simultaneous regulation of inert or inhibiting flowing gases between the reactor inlet and the reactor outlet enables high-speed gas flow switching.

The process of the present disclosure may also be used in some other reactor configurations. For example, single wafer ALD reactors for semiconductor processing may have different gas flow configurations. A "cross-flow" reactor has parallel gas flows across the wafer surface. The "showerhead" reactor introduces gases into the reactor through a distribution plate in a manner perpendicular to the wafer surface. The gas then flows radially over the entire wafer surface. Other differences between ALD reactors may include hot wall and cold wall reactors. In a "hot wall" reactor, the walls, gases, and substrates in the reactor are all heated to the temperature of the walls. In a "cold wall" reactor, only the substrate is heated, while the wall is maintained at room temperature or heated only slightly.

Other ALD reactors may deposit on many samples simultaneously. These reactors are also referred to as "batch" reactors. It can coat a plurality of samples at the same time and can greatly shorten the time required for coating one sample. Batch reactors can improve the cost and time efficiency of commercial ALD processes. The reactant and purge time constants are longer in batch reactors due to the larger reactor volume and the lower gas conductance (gas con-ductance) between the multiple samples. However, the advantages of multitasking may compensate for longer time constants.

Inductively Coupled Plasma (ICP) is a common plasma source during plasma ALD. The plasma is typically operated at a pressure of about 100 and 500 mTorr. Plasma enhanced ALD is performed without the use of an inert carrier gas during the plasma reaction cycle. However, an inert carrier gas or suppression precursor of the present disclosure may be used to alternate the plasma reaction cycle with a conventional reactant ALD cycle.

A schematic diagram of an exemplary ICP plasma reactor 600 for carrying out certain disclosed embodiments is shown in fig. 6. The reactor 600 includes component parts as shown and designated in the figure. These components include, for example, a gas source 601, a metal precursor and inhibitor source 602, a first leak valve 603, a reactor chamber 604, a quartz tube 605, an inlet control valve 606, an RF coil 607, a second leak valve 608, a turbo pump 609, and a Quadrupole Mass Spectrometry (QMS) module 610. The suppression precursor 602 may be selectively admitted to the reactor chamber 604 via the inlet control valve 606 according to any of the methods described herein.

The methods of the present disclosure may also be performed in a Capacitively Coupled Plasma (CCP) system. Typical CCP systems are driven by a single Radio Frequency (RF) power supply (typically at about 13.56 MHz). One of the two electrodes is connected to a power source, while the other is grounded. Since this configuration is similar in principle to a capacitor in a circuit, the plasma formed in this configuration is referred to as a capacitively coupled plasma. An exemplary CCP system for performing the present method may include single station modules or multi-station modules (also referred to as quad stations).

When an electric field is generated between the electrodes, the atoms are ionized and release electrons. Electrons in the gas are accelerated via the RF field and can ionize the gas directly or indirectly by collisions to produce secondary electrons. When the electric field is strong enough, it can cause so-called electron bursts. After avalanche breakdown, the gas becomes conductive due to sufficient free electrons. Which is usually accompanied by light emission from excited atoms or molecules in the gas.

A schematic diagram of an exemplary CCP processing reactor for performing certain disclosed embodiments is illustrated in fig. 8. The figure depicts a schematic diagram of an embodiment of an Atomic Layer Deposition (ALD) processing station 800 having a chamber body 802 for maintaining a low pressure environment. Multiple ALD processing stations 800 may be included in a common low pressure processing tool environment. In some implementations, one or more hardware parameters of the ALD processing station 800, including those discussed in detail below, may be programmatically adjusted by one or more computer controllers 850 (also discussed further below).

The ALD processing station 800 is in fluid communication with a delivery system 801a for delivering process gases to a distribution showerhead 806. The reactant delivery system 801a includes a mixing vessel 804 for mixing and/or conditioning a process gas, such as a metal amide, metal alkoxide, or silicon amide gas, or an inhibiting precursor gas as defined above, for delivery to a showerhead 806. One or more mixing vessel inlet valves 820 may control the introduction of process gases into the gas mixing vessel 804.

For example, the embodiment of fig. 8 includes a vaporization point 803 for vaporizing a liquid reactant to be supplied to a mixing vessel 804. In some embodiments, the vaporization point 803 may be a heated vaporizer. Saturated reactant vapors produced from the vaporizer may condense in downstream transfer lines. In some embodiments, the transfer line downstream of the vaporization point 803 may be hot traced. In some examples, mixing vessel 804 may also be hot-traced. In a non-limiting example, the line downstream of the vaporization point 803 has an increasing temperature profile that extends from about 100 ℃ to about 150 ℃ at the mixing vessel 804.

In some embodiments, a liquid precursor, or a liquid suppression precursor, or a liquid reactant may be vaporized at the liquid injector. For example, the liquid injector may inject pulses of liquid reactants into the carrier gas stream upstream of the mixing vessel. In one embodiment, the liquid injector may vaporize the reactants by rapidly vaporizing liquid from high to low pressure. In another example, the liquid injector may atomize the liquid into discrete droplets, which are then vaporized in the heated delivery line. Smaller droplets may vaporize faster than larger droplets, which results in a reduced delay between liquid injection and complete vaporization. Faster vaporization may result in a reduced length of line downstream of vaporization point 803. In one version, the liquid injector may be mounted directly on the mixing vessel 804. In another aspect, the liquid injector may be mounted directly on the spray head 806.

The showerhead 806 distributes process gas to the substrate 812. In the embodiment shown in FIG. 8, the substrate 812 is located below the showerhead 806 and is shown disposed on the pedestal 808. The showerhead 806 may have any suitable shape and may have any suitable number and configuration of ports for distributing the process gases to the substrate 812. In some implementations, the pedestal 808 can be raised or lowered to expose the substrate (or wafer) 812 to the volume between the substrate 812 and the showerhead 806.

It is understood that in some embodiments, the base height may be programmatically adjusted by a suitable computer controller 850. In another aspect, adjusting the height of the pedestal 808 may enable changing the plasma density during plasma activation in the process of the plasma ignited embodiment. After the processing stage is completed, the pedestal 808 may be lowered during another substrate transfer stage to enable the substrate 812 to be removed from the pedestal 808. In some embodiments, the pedestal 808 may be temperature controlled via a heater 810. In some embodiments, the pedestal 808 may be heated to a temperature between about 25 ℃ to about 400 ℃, or between about 200 ℃ to about 300 ℃, during selective deposition of a film, as described in the disclosed embodiments. In some embodiments, the susceptor is set at a temperature between about 25 ℃ to about 400 ℃, or between about 200 ℃ to about 300 ℃.

Additionally, in some embodiments, pressure control for the processing station 800 may be provided via a butterfly valve 818. As shown in the embodiment of fig. 8, butterfly valve 818 regulates the vacuum provided by a downstream vacuum pump (not shown). However, in some embodiments, the pressure control of the processing station 800 may also be adjusted by changing the flow rate of one or more gases introduced to the processing station 800.

In some embodiments, the position of the showerhead 806 may be adjusted relative to the pedestal 808 to change the volume between the substrate 812 and the showerhead 806. Additionally, it should be understood that the vertical position of the pedestal 808 and/or showerhead 806 may be changed by any suitable mechanism within the scope of the present disclosure. In some implementations, the pedestal 808 can include an axis of rotation for turning the direction of the substrate 812. It is to be understood that in some embodiments, one or more of these exemplary adjustments may be performed programmatically by one or more suitable computer controllers 850.

In some embodiments, in which a plasma may be used as described above, the showerhead 806 and the pedestal 808 are in electrical communication with a Radio Frequency (RF) power supply 814 and a matching network 816 to capacitively power the plasma. In some embodiments, the plasma energy may be controlled by controlling one or more of the process station pressure, gas concentration, RF source power, RF source frequency, and plasma power pulse timing. For example, the RF power supply 814 and matching network 816 may be operated at any suitable power to form a plasma having a desired radical species composition. The low plasma power may be selected to prevent sputtering of materials on the substrate surface. An exemplary suitable power is about 150W to about 6000W.

The RF power supply 814 may provide RF power at any suitable frequency. The RF power supply 814 may be configured to control the high frequency and low frequency RF power sources independently of each other. Exemplary low frequency RF frequencies may include, but are not limited to, frequencies between 0kHz and 500 kHz. Exemplary high frequency RF frequencies may include, but are not limited to, frequencies between 1.8MHz and 2.45GHz, or greater than about 13.56MHz, or greater than 27MHz, or greater than 40MHz, or greater than 60 MHz. It is to be understood that any suitable parameter may be adjusted, either discretely or continuously, to provide plasma energy for surface reactions.

The present disclosure also includes an exemplary method. In one example, referring to fig. 9, a method 900 of profile control in metal oxide deposition comprises: at 902, a precursor gas is admitted to a chamber of an ALD reactor at a first gas flow rate in a first zone of a plurality of zones in the chamber to form a first film at a first deposition rate; and, at 904, delivering an inhibiting precursor gas at a second gas flow rate in the same or a second region of the plurality of regions in the chamber to inhibit growth of the first film.

In some examples, the method 900 includes: the suppression precursor gas is delivered into the chamber prior to entry of the precursor gas into the chamber. In some examples, the method 900 includes: the precursor gas is delivered into the chamber prior to the suppressing precursor gas entering the chamber. In some examples, the method 900 includes: the precursor gas is inhibited from being delivered into the chamber while the precursor gas is being admitted into the chamber. In some examples, the method 900 includes: a second precursor gas is delivered in one of the plurality of zones at a third gas flow rate to form a second film at a second deposition rate. In some examples, the method 900 includes: a second precursor gas is delivered while a suppressing precursor gas is admitted to the chamber. In some examples, the precursor gas comprises a chelating agent. In some examples, the chelating agent comprises one or more of HAcAc, butane thiol, ethanol, and phosphine. In some examples, the method 900 includes: the low exposure inhibited precursor gas is delivered at an exposure level of less than 1% of the minimum exposure required to achieve precursor gas saturation on a flat surface. In some embodiments, the operations of method 900 are performed in a different order.

Referring to fig. 10, an exemplary method 1000 for profile control in metal oxide deposition includes: at 1002, a substrate is provided to a process chamber; at 1004, exposing the substrate to the precursor to form a film on the substrate; at 1006, the process chamber is optionally purged; at 1008, exposing the substrate to an inhibiting precursor to inhibit growth of at least a portion or a profile of a film on the substrate; at 1010, optionally purging the process chamber; at 1012, it is determined whether a desired film thickness or profile has been produced. If not, operations 1004 and 1012 are repeated with sufficient cycles until a film of a desired thickness or profile is formed.

In some examples, the method 1000 includes: the suppression precursor is delivered into the process chamber prior to entry of the precursor into the process chamber. In some examples, the method 1000 includes: the precursor is delivered to the process chamber prior to entering the suppression precursor into the chamber. In some examples, the method 1000 includes: the suppression precursor is delivered into the process chamber while the precursor is being admitted into the chamber. In some examples, the method 1000 includes: a second precursor is delivered in one of the plurality of zones to form a second film at a second deposition rate. In some examples, the method 1000 includes: a second precursor is delivered while a suppression precursor is entering the chamber. In some examples, the precursor comprises a chelating agent. In some examples, the chelating agent comprises one or more of HAcAc, butane thiol, ethanol, and phosphine. In some examples, the method 1000 includes: the low exposure inhibiting precursor is delivered at an exposure level of less than 1% of the minimum exposure required to achieve precursor saturation on the substrate.

In some embodiments, the operations of method 1000 are performed in a different order, e.g., the substrate may be exposed to an inhibition precursor before exposure to the precursor.

In some examples, the non-transitory machine-readable medium 1122 contains instructions that, when read by a machine (e.g., the computer controller 1100), cause the machine to perform the following operations: including at least the non-limiting exemplary operations of methods 900 and 1000 outlined above.

FIG. 11 is an exemplary block diagram illustrating a computer controller 1100, on which one or more of the exemplary process embodiments described herein may be implemented or by which one or more of the exemplary process embodiments described herein may be controlled by the computer controller 1100. In alternative embodiments, the machine 1100 may operate as a standalone device or may be connected (e.g., networked) to other machines. In a network arrangement, the computer controller 1100 may operate in the capacity of a server machine, a client machine, or both, in a server-client network environment. In an exemplary implementation, computer controller 1100 can operate as a peer machine in a peer-to-peer (P2P) network (or other distributed network) environment. Moreover, while only a single computer controller 1100 is shown, the term "machine" shall also be taken to include any collection of machines that individually or jointly execute a set (or multiple sets) of instructions to perform any one or more of the methodologies discussed herein, such as via cloud computing, software as a service (SaaS), or other computer cluster configuration.

The examples described herein may include, or be operable with, logic, components, or mechanisms. A circuit system is a collection of circuits implemented in a tangible entity that includes hardware (e.g., simple circuits, gates, logic, etc.). The circuitry components may have flexibility over time and basic hardware variability. The circuitry includes components that, alone or in combination, can perform specified operations when performing operations. In an example, the hardware of the circuitry may be designed in a fixed and immutable manner to perform certain operations (e.g., hardwired). In an example, the hardware of the circuitry may include variably connected physical components (e.g., execution units, transistors, simple circuits, etc.) including a computer readable medium modified via physical means (e.g., magnetically, electrically, by a movable arrangement of invariant mass particles, etc.) to encode instructions for a particular operation. When physical components are connected, the basic electrical properties of the hardware components are caused to change (e.g., from an insulator to a conductor, and vice versa). The instructions enable embedded hardware (e.g., an execution unit or loading mechanism) to generate components of circuitry in the hardware via a variable connection to perform portions of particular operations when the operations are performed. Thus, when the apparatus operates, the computer readable medium is communicatively coupled to other components of the circuit. In an example, any of the physical components may be used in more than one component in more than one circuitry. For example, in operation, an execution unit may be used in a first circuit of a first circuitry at a point in time and reused by a second circuit of the first circuitry, or by a third circuit of the second circuitry, at a different time.

A computer controller (e.g., computer system) 1100 may include a hardware processor 1102 (e.g., a Central Processing Unit (CPU), a hardware processor core, or any combination thereof), a Graphics Processing Unit (GPU)1103, a main memory 1104, and a static memory 1106, some or all of which may communicate with each other via an interconnect (e.g., bus) 1108. The computer controller 1100 may also include a display apparatus 1110, an alphanumeric input device 1112 (e.g., a keyboard), and a User Interface (UI) navigation device 1114 (e.g., a mouse). In an example, the display apparatus 1110, the alphanumeric input device 1112, and the UI navigation device 1114 may be touch screen displays. The computer controller 1100 may additionally include a mass storage device (e.g., drive unit) 1116, a signal generation device 1118 (e.g., a speaker), a network interface device 1120, and one or more sensors 1121, such as a Global Positioning System (GPS) sensor, compass, accelerometer, or another sensor. The computer controller 1100 may include an output controller 1128 (e.g., a serial (e.g., Universal Serial Bus (USB)), parallel, or other wired or wireless (e.g., Infrared (IR), Near Field Communication (NFC), etc.) connection) to communicate with or control one or more peripheral devices (e.g., a printer, a card reader, etc.).

The mass storage 1116 may include a machine-readable medium 1122 on which one or more sets of data structures or instructions 1124 (e.g., software) may be stored, the data structures or instructions 1124 implementing or being used by any one or more of the techniques or functions described herein. The instructions 1124 may also reside, completely or at least partially, within the main memory 1104, within the static memory 1106, within the hardware processor 1102, or within the GPU1103 (during execution thereof by the computer controller 1100). In an example, one or any combination of the hardware processor 1102, the GPU1103, the main memory 1104, the static memory 1106, or the mass storage 1116 may constitute a machine-readable medium.

While the machine-readable medium 1122 is shown to be a single medium, the term "machine-readable medium" can include a single medium, or multiple media (e.g., a centralized or distributed database, and/or associated caches and servers) configured to store the one or more instructions 1124.

The term "machine-readable medium" may include: any medium that can store, encode, or carry instructions 1124 for execution by the computer controller 1100, and that cause the computer controller 1100 to perform any one or more of the techniques of this disclosure; or any medium that can store, encode, or carry data structures used by or associated with such instructions 1124. Non-limiting examples of machine readable media may include solid state memory and optical and magnetic media. In an example, a mass machine-readable medium includes machine-readable medium 1122 having a plurality of particles with a constant mass (e.g., a static mass). Thus, a mass machine-readable medium is not a transitory propagating signal. Specific examples of mass machine-readable media can include non-volatile memory, such as semiconductor memory devices (e.g., electronically programmable read-only memory (EPROM), electronically erasable programmable read-only memory (EEPROM), and flash memory devices, magnetic disks such as internal hard disks and removable disks, magneto-optical disks, and CD-ROM and DVD-ROM disks.

Although embodiments have been described with reference to specific exemplary embodiments, it will be evident that various modifications and changes may be made to these embodiments without departing from the broader spirit and scope of the invention. The specification and drawings are, accordingly, to be regarded in an illustrative rather than a restrictive sense. The accompanying drawings that form a part hereof show by way of illustration, and not of limitation, specific embodiments in which the subject matter may be practiced. The embodiments shown are described in sufficient detail to enable those skilled in the art to practice the teachings disclosed herein. Other embodiments may be utilized and derived therefrom, such that structural and logical substitutions and changes may be made without departing from the scope of this disclosure. The specific embodiments are therefore not to be considered in a limiting sense, and the scope of various embodiments is defined only by the appended claims, along with the full range of equivalents to which such claims are entitled.

Such embodiments of the inventive subject matter may be referred to herein, individually and/or collectively, by the term "invention" merely for convenience and without intending to voluntarily limit the scope of this application to any single invention or inventive concept if more than one is in fact disclosed. Thus, although specific embodiments have been illustrated and described herein, it should be appreciated that any arrangement calculated to achieve the same purpose may be substituted for the specific embodiments shown. This disclosure is intended to cover any and all adaptations or variations of various embodiments. Combinations of the above embodiments, and other embodiments not specifically described herein, will be apparent to those of skill in the art upon reviewing the above description.