Semiconductor vapor phase etching apparatus with intermediate chamber

Abstract

To provide a semiconductor processing device with an intermediate chamber.SOLUTION: A system configuration 1 of a semiconductor processing device during a filling stage comprises an intermediate chamber 4 between a reactant source 3 and a reactor 5. Etch reactant vapor is pulsed from the intermediate chamber to the reactor to etch a substrate. In addition, a control system 7 controls the pulse width and timing of the pulsing to the reactor 5.SELECTED DRAWING: Figure 2

Description

[Technical Field]

[0001] Incorporation by reference of all priority applications This application claims priority to U.S. Provisional Patent Application No. 62 / 875,910, filed July 18, 2019, the contents of which are incorporated herein by reference in their entirety for all purposes. [Background technology]

[0002] The technical field relates to semiconductor processing equipment with intermediate chambers, and more particularly to etching reactors with intermediate chambers.

[0003] 2. Description of Related Art Controlled removal of material in semiconductor processing is highly desirable. While chemical vapor etching (CVE) or atomic layer etching (ALE) can have advantages over plasma systems, it is difficult for both thermal and plasma etching to provide uniform etching across a large substrate, especially when the substrate has significant topology. Summary of the Invention

[0004] According to one aspect, a semiconductor etching apparatus is disclosed that can include a reaction chamber, an intermediate chamber upstream of and in fluid communication with the reaction chamber, the intermediate chamber configured to deliver an etching reactant vapor to the reaction chamber, a source of etching reactant vapor upstream of and in fluid communication with the intermediate chamber, the source configured to deliver the etching reactant vapor to the intermediate chamber, a first valve disposed along a reactant supply line between the source and the intermediate chamber, the first valve configured to adjust a flow rate of the etching reactant vapor to the intermediate chamber, and a second valve disposed along the reactant supply line between the intermediate chamber and the reaction chamber, the second valve configured to adjust a flow rate of the etching reactant vapor to the reaction chamber.

[0005] According to one aspect, a semiconductor etching apparatus is disclosed. The apparatus can include a reaction chamber, an intermediate chamber upstream of and in fluid communication with the reaction chamber, the intermediate chamber configured to deliver an etching reactant vapor to the reaction chamber, and a control system configured to pulse the etching reactant vapor from the intermediate chamber into the reaction chamber.

[0006] According to one aspect, a method of etching a substrate is disclosed that can include supplying an etching reactant vapor to an intermediate chamber and pulsing at least a portion of the etching reactant vapor from the intermediate chamber to a reaction chamber downstream from the intermediate chamber. [Brief explanation of the drawings]

[0007] These and other features, aspects and advantages of the present invention will now be described with reference to drawings of several embodiments that are intended to illustrate, not limit, the invention.

[0008] [Figure 1] FIG. 1 is a schematic system diagram of a semiconductor processing apparatus during a fill stage, according to various embodiments. [Figure 2] FIG. 2 is a schematic system diagram of a semiconductor processing apparatus during a pulse mode of a first example, according to one embodiment. [Figure 3] FIG. 3 is a schematic system diagram of a semiconductor processing apparatus during a pulse mode of a second example, according to one embodiment. [Figure 4] FIG. 4 is a schematic system diagram of a semiconductor processing apparatus during pulse mode in a third example, according to one embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0009] Submonolayers or more of material can be removed from substrates by chemical vapor etching (CVE). Pulsing the gas-phase etching reactants (e.g., adsorbed reactants and / or etchants) provides additional parameters to tailor and control the etching process and achieve desired distribution across large substrates used in advanced semiconductor processing. Some pulsed etching processes use one or more gas-phase reactants in sequential pulses. For example, a reactant may adsorb a second reactant in one pulse, followed by a second reactant forming volatile byproducts containing adatoms, and several atoms from the surface being etched. In this way, etching of desired materials on the substrate surface can be carefully controlled. Another system and method for such pulsed and cyclic etching processes is described in U.S. Pat. No. 10,273,584, the contents of which are incorporated herein by reference in their entirety for all purposes.

[0010] Thermochemical etching of microelectronic materials can be superior to plasma etching processes. However, to have a uniform etch rate across the wafer, the partial pressure, residence time, and temperature of the etching reactants (e.g., etchants and / or other reactants) and byproducts must not vary spatially across the wafer. Even when surface control is lacking in the etching reaction, the etching per cycle (EPC) can be controlled, for example, by dose starvation. Dose starvation involves limiting the number of molecules injected into the reactor in each etching pulse or cycle, which also limits the depth of penetration into the substrate. Therefore, pulsed etching with precise dose control can work, regardless of whether multiple reactants are involved, and can provide better etching process control. However, to uniformly etch large-area substrates, the dose should preferably be evenly distributed across the substrate.

[0011] A system configuration using a pulsing method in which the total dose and partial pressure during a pulse can be independently controlled can be useful for uniformly etching large-area substrates. While the dose can determine the EPC of the process, the behavior of the partial pressure during the pulse can determine the etching uniformity. In some embodiments, partial / total pressure pulsing is used instead of continuous flow etching. Pulsing the etching reactants into the reactor can increase the convective and diffusive transport rates within the reactor. Therefore, it can result in a more conformal etch than a continuous flow (steady-state) etching process.

[0012] 1-4 illustrate system configuration 1 incorporating various pulsing techniques. In some embodiments, system configuration 1 includes a carrier gas line 2, a reactant source 3 downstream of and in fluid communication with carrier gas line 2, an intermediate chamber 4 downstream of source 3, a reactor 5 downstream of intermediate chamber 4, and multiple valves V1, V2, and V3. A reactant supply line 6 connects source 3 to intermediate chamber 4, and valve V1 is attached to reactant supply line 6 between source 3 and intermediate chamber 4. The reactant supply line 6 connects intermediate chamber 4 to reactor 5, and multiple valves V2 and V3 are attached to line 6 between intermediate chamber 4 and reactor 5. Valves V1, V2, and V3 can comprise any suitable type of valve. For example, in various embodiments, valves V1 and V2 can comprise adjustable valves having multiple flow conductances. In some embodiments, valves V1 and V2 can comprise binary on / off valves. In some embodiments, valve V3 can comprise a needle valve that can be adjusted to a desired flow conductance. As shown in FIGS. 1-4 , control system 7 can comprise processing circuitry configured to control the operation (e.g., opening and closing) of valves V1, V2, and V3 and / or the operation of other components of the system, such as reactor components. Although not illustrated, control system 7 can also be in electrical communication with various types of sensors, such as pressure sensors configured to monitor the pressure of intermediate chamber 4, source 3, reactor 5, or any other suitable component or gas line of the system. Control system 7 can also be in electrical communication with other components, such as heaters. Additionally, although not illustrated, system 1 can include filters, for example, upstream of intermediate chamber 4 and / or upstream of any of valves V1, V2, and V3.

[0013] In some embodiments, source 3 comprises a vaporizer configured to convert a liquid or solid material into a vapor. For example, source 3 can comprise a bubbler, evaporator, liquid injector, solid source sublimator, etc. Source 3 can supply vaporized reactant to reactant supply line 6. In various embodiments, source 3 can include reactants (e.g., etchants) for an etching process. A carrier gas can be used with the vaporizer as shown, and can also be used to carry / dilute the natural gas reactant. In other embodiments, a carrier gas is not used.

[0014] In some embodiments, system configuration 1 does not include a source of plasma, radicals, or excited species. In some embodiments, system configuration 1 does not include an RF, microwave, or ICP source for plasma, radical, or excited species formation. In some embodiments, system configuration 1 is not compatible and cannot be used for plasma-based processes.

[0015] FIG. 1 illustrates system 1 in a filling stage, where vaporized reactants are delivered to and held within intermediate chamber 4. For example, in FIG. 1, valve V1 can be opened to allow intermediate chamber 4 to be filled to a desired pressure with a mixture of carrier gas and vaporized reactants. In some embodiments, valve V1 can be an adjustable valve capable of controlling the flow conductance of the vaporized reactants. Intermediate chamber 4 can comprise a chamber capable of ensuring that the reactants remain in vapor form for delivery to reactor 5. In some embodiments, control system 7 can also measure or control the amount of reactant vapor delivered to reactor 5, for example, by opening or closing one or more of valves V1 and V2. Thus, control system 7 can be configured to control the pulse width and timing of pulse delivery to reactor 5. In some embodiments, pulses to reactor 5 can have pulse widths ranging from about 0.001 seconds to 60 seconds. For example, the pulse width can be in the range of about 0.01 seconds to 10 seconds, about 0.05 seconds to 10 seconds, or about 0.1 seconds to 5 seconds. In some embodiments, the partial pressure associated with the pulse height of the pulse can be in the range of about 0.001 mbar to 100 mbar. For example, the partial pressure associated with the pulse height of the pulse can be in the range of about 0.05 mbar to 50 mbar, or in the range of about 0.1 mbar to 20 mbar. Valve V2 can be opened to supply a mixture of carrier gas and vaporized reactant to reactor 5. In some embodiments, valve V2 can be an adjustable valve that can control the flow conductance of the vaporized reactant. In some embodiments, valve V3 can be a needle valve that controls the flow conductance of the vaporized reactant.

[0016] In some embodiments, the system configuration 1 can include one or more thermal zones maintained at various temperatures by heaters or other heating devices. In some embodiments, there are separate thermal zones for the vaporizer, intermediate chamber 4, and reaction chamber, each having a first, second, and third temperature, respectively. In some embodiments, the first, second, and third temperatures are approximately equal. In some embodiments, the second temperature of the second thermal zone can be higher than the first temperature of the first thermal zone. In various embodiments, for example, the second temperature can be higher than the first temperature by a temperature difference ranging from 5°C to 50°C, from 5°C to 35°C, or from 10°C to 25°C. In some embodiments, the first temperature of the first thermal zone can be higher than the second temperature of the second thermal zone. In some embodiments, a heater jacket can be provided over a portion of the carrier gas line 2 to maintain the line 2 at or above the temperature of its respective thermal zone and above the condensation temperature of the reactants.

[0017] System 1 can operate in various etching modes. In FIG. 1, intermediate chamber 4 can be filled with vaporized reactant and carrier gas to a desired or setpoint pressure, which can correlate to the desired reactant partial pressure. Reactant vapor can be vaporized in source 3. When valve V1 is opened, a mixture of vaporized reactant and carrier gas can be carried and delivered to intermediate chamber 4 along reactant supply line 6. As shown in FIGS. 2-3, intermediate chamber 4 can be filled to a pressure of P1, and valve V1 can be closed. The dose of vaporized reactant in intermediate chamber 4 can be determined by the equation nR=P1V / T.

[0018] FIG. 2 illustrates a first etching mode in which pulses of a first type or shape are delivered to reactor 5. As described above, valve V1 can be closed and valve V2 can be at least partially open. A portion of the dose of reactant vapor contained in intermediate chamber 4 can be delivered to reactor 5. The partial pressure of the reactant during the pulse can be determined, at least in part, by the conductance of needle valve V3 and the pressure difference between the pressure in intermediate chamber 4, P1, and the pressure in reactor 5, P2. In some embodiments, pressure P1 can be in the range of about 0.001 mbar to 100 mbar. For example, pressure P1 can be in the range of about 0.05 mbar to 50 mbar, or in the range of about 0.1 mbar to 20 mbar. In some embodiments, pressure P2 can be in the range of about 0.001 mbar to 100 mbar. For example, pressure P2 can be in the range of about 0.05 mbar to 50 mbar, or in the range of about 0.1 mbar to 20 mbar. In various embodiments, the ratio of P1 to P2 can be less than about 100:1, 50:1, 10:1, 5:1, 3:1, 2:1, 1.5:1, 1.25:1, or 1.1:1. The pressure difference is determined by the formula ΔP = P1 - P2. During operation, the pressure difference ΔP changes constantly as pressure P1 decreases after opening valve V2. Therefore, the partial pressure of the reactants in reaction chamber 5 can also change as a function of time and can be linear if the conductance is held constant during the pulse. As shown in FIG. 2, the precursor tail at the end of the pulse can be caused by precursor gas escaping from the volume between V2 and V3 after shutting off V2. In some embodiments, the partial pressure in the second half of the pulse is less than about 75% of the maximum partial pressure in the first half of the pulse. In other embodiments, the partial pressure in the second half of the pulse is less than about 50% of the maximum partial pressure in the first half of the pulse. In another embodiment, the partial pressure in the second half of the pulse is less than about 25% of the maximum partial pressure in the first half of the pulse. The exemplary pulses can be repeated periodically in a pulsed or cyclic chemical vapor etching process.

[0019] FIG. 3 illustrates a second etching mode in which pulses of a second type or shape are delivered to the reactor 5. Unlike the first mode of FIG. 2, in which only a portion of the fill volume of the intermediate chamber 4 is used, in the second mode of FIG. 3, all or substantially all of the reactant vapor filling the intermediate chamber 4 may be used, e.g., delivered to the reaction chamber 5. As shown in FIG. 3, valve V1 may be closed. Valve V2 may be opened, and at least a portion of the dose of reactant vapor contained within the intermediate chamber 4 may be delivered to the reactor 5 until the pressure between the fill volume (e.g., the intermediate chamber 4) and the reactor 5 is the same (ΔP=0). The partial pressure of the vaporized reactant during this pulse period may be determined by the conductance of needle valve V3 and the pressure difference between the pressure P1 in the intermediate chamber 4 and the pressure P2 in the reactor 5. The pressure difference is determined by the equation ΔP=P1-P2. During operation, the pressure difference ΔP may constantly change as the pressure P1 decreases after opening valve V2. Thus, the partial pressure of the reactant delivered to the reaction chamber 5 can also vary linearly over time if the conductance is held constant. As shown in FIG. 3, the partial pressure of the vaporized reactant can decrease linearly after opening valve V2. In some embodiments, the partial pressure can decrease at a rate greater than 10% per second. For example, the partial pressure can decrease at a rate greater than about 25% per second, greater than about 50% per second, or greater than about 75% per second. In various embodiments, the partial pressure of the vaporized reactant can decrease approximately linearly after opening valve V2. Unlike the first mode shown in FIG. 2, in the second mode of FIG. 3, this pulsed mode may lack a partial pressure tail. The dose of the vaporized reactant can be determined by the formula [P1(0)-P2]V / T, where P1(0) is the pressure in the intermediate chamber 4 before opening V2 and P2 is the reactor pressure. The exemplary pulses can be repeated periodically in a pulsed or cyclic chemical vapor etching process.

[0020] FIG. 4 illustrates a third etching mode in which a third type or shape of pulse is delivered to reactor 5. In the third mode shown in FIG. 4, both V1 and V2 are open during the pulse, thereby transporting vaporized reactant from source 3 through intermediate chamber 4 to reactor 5. The partial pressure of the reactant during the pulse time can be determined, at least in part, by the pressure in source vessel 3 and the conductance of needle valve V3. If the vaporization rate and conductance of the precursor in source vessel 3 remain constant during the pulse, the partial pressure can also remain constant during the pulse. For reasons generally similar to those discussed above with respect to the precursor tail in FIG. 2, a precursor tail may also be present at the end of the pulse, as shown in FIG. 4. The example pulse can be repeated periodically in a pulsed or cyclic chemical vapor etching process. While operation of this third etching mode may not be affected by the presence of an intermediate chamber compared to an apparatus without such a chamber, it illustrates the adaptability of the apparatus's operation to achieve these and other desired modes and provide another variable to adjust to achieve a desired etch distribution and effect across the substrate within the reaction chamber. In another embodiment, operation of this third etching mode may be affected by the presence of an intermediate chamber compared to an apparatus without such a chamber, but demonstrates the flexibility of the apparatus' operation to achieve these and other desired modes and provide another variable to adjust to achieve the desired etching distribution and effect across the substrate within the reaction chamber.

[0021] Beneficially, the systems and methods disclosed herein can provide improved spatial uniformity and conformality in various types of etching, such as ALE procedures. The use of an intermediate chamber 4 with valves V1, V2, and V3 between the source 3 and the reactor 5 can provide control of the overall dose and partial pressure during the pulse. Different pulse modes can also be selected to provide desired pulse shapes to the reactor 5.

[0022] Although specific embodiments of the present invention have been described, these embodiments are presented by way of example only and are not intended to limit the scope of the present disclosure. Indeed, the novel methods and systems described herein may be embodied in a variety of other forms. Furthermore, various omissions, substitutions, and modifications may be made in the systems and methods described herein without departing from the spirit of the present disclosure. The appended claims and their equivalents are intended to cover such forms or modifications as are within the scope and spirit of the present disclosure. Accordingly, the scope of the present invention is defined solely by reference to the appended claims.

[0023] Any feature, material, characteristic, or grouping described in connection with a particular aspect, embodiment, or example should be understood to be applicable to any other aspect, embodiment, or example described in this section or elsewhere in this specification, unless inconsistent therewith. All features disclosed herein (including the accompanying claims, abstract, and drawings), and / or all steps of any method or process so disclosed, may be combined in any combination, except combinations in which at least some of such features and / or steps are mutually exclusive. Protection is not limited to the details of all foregoing embodiments. Protection extends to any novel or novel combination of features disclosed herein (including the accompanying claims, abstract, and drawings), or any novel or novel combination of steps of any method or process so disclosed.

[0024] Furthermore, certain features that are described in this disclosure in the context of separate embodiments can also be implemented in combination in a single embodiment. Conversely, various features that are described in the context of a single embodiment can also be implemented in multiple embodiments separately or in any suitable subcombination. Furthermore, while features are described above as functioning in a particular combination, one or more features from a claimed combination can optionally be deleted from the combination, and the combination may be claimed as a subcombination or a variation of the subcombination.

[0025] Furthermore, while operations may be depicted in the figures or described herein in a particular order, such operations need not be performed in the particular order or sequentially shown, nor need all operations be performed, to achieve desirable results. Other operations not shown or described may be incorporated into the example methods and processes. For example, one or more additional operations may be performed before, after, simultaneously with, or between any of the described operations. Furthermore, in other embodiments, operations may be rearranged or reordered. Those skilled in the art will appreciate that in some embodiments, the actual steps performed in the illustrated and / or disclosed processes may differ from those shown in the figures. Depending on the embodiment, some of the above steps may be eliminated, and other steps may be added. Furthermore, the features and attributes of the specific embodiments disclosed above may be combined in different ways to form additional embodiments, all of which are within the scope of the present disclosure. Also, the separation of various system components in the above embodiments should not be understood to require such separation in all embodiments. And, it should be understood that the described components and systems may generally be integrated together in a single product or packaged into multiple products.

[0026] For purposes of this disclosure, certain aspects, advantages, and novel features have been described herein. Not necessarily all such advantages will be achieved in accordance with any particular embodiment. Thus, for example, one skilled in the art will recognize that the present disclosure can be embodied or carried out in a way that achieves one advantage or group of advantages taught herein, without necessarily achieving other advantages that may be taught or suggested herein.

[0027] It will be understood that conditional language, such as "can," "could," "might," and "may," is generally intended to convey that certain embodiments include certain features, elements, and / or steps, while other embodiments do not, unless otherwise specified or understood within the context in which it is used. Thus, such conditional language is not generally intended to suggest that features, elements, and / or steps are somehow required in one or more embodiments, or that one or more embodiments necessarily include logic for determining whether those features, elements, and / or steps are included in or performed in any particular embodiment, with or without user input or direction.

[0028] Conjunctions, such as the phrase "at least one of X, Y, and Z," unless otherwise indicated, are understood in the context in which they are otherwise commonly used to convey that an item, term, etc. is either X, Y, or Z. Thus, such conjunctive language is not generally intended to suggest that a particular embodiment requires the presence of at least one of X, at least one of Y, and at least one of Z.

[0029] As used herein, terms of degree, such as the terms "approximately," "about," "generally," and "substantially," refer to a value, amount, or characteristic that is close to a stated value, amount, or characteristic that still performs a desired function or achieves a desired result. For example, the terms "approximately," "about," "generally," and "substantially" can refer to an amount that is within 10%, 5%, 1%, 0.1%, and 0.01% of a stated amount. As another example, in certain embodiments, the terms "generally parallel" and "substantially parallel" refer to a value, amount, or characteristic that is 15 degrees, 10 degrees, 5 degrees, 3 degrees, 1 degree, or 0.1 degrees or less away from exact parallelism.

[0030] The scope of the present disclosure is not intended to be limited by the specific disclosure of preferred embodiments in this section or elsewhere herein, and can be defined by the claims presented in this section or elsewhere herein, or presented in the future. Claim terms are to be interpreted broadly based on the terms used in the claims, and not limited to the examples described herein or during prosecution, which examples are to be construed as non-limiting.

Claims

1. An atomic layer etching apparatus for removing a layer of material from a substrate, comprising: a reaction chamber; an intermediate chamber upstream of and in fluid communication with the reaction chamber, the intermediate chamber configured to deliver an etching reactant vapor to the reaction chamber; a source of etching reactant vapor upstream of the intermediate chamber and in fluid communication with the intermediate chamber, the source configured to deliver the etching reactant vapor to the intermediate chamber; a first valve disposed along a reactant supply line between the source and the intermediate chamber, the first valve configured to adjust the flow rate of the etching reactant vapor into the intermediate chamber; a second valve disposed along the reactant supply line between the intermediate chamber and the reaction chamber, the second valve configured to adjust the flow rate of the etching reactant vapor into the reaction chamber; a third valve between the second valve and the reaction chamber, the third valve having a plurality of adjustable flow conductances, the third valve including a needle valve configured to be adjusted to a set flow conductance; a control system configured to control operation of the first valve, the second valve, and the reaction chamber, the control system configured to control a partial pressure of the etching reactant vapor based at least in part on a flow conductance of the third valve; the control system is configured to control the removal of a layer of material from a substrate by pulsing the etching reactant vapor into the reaction chamber; In a first etching mode, the control system is configured to direct the first valve to close and the second valve to open in each pulse to deliver only a portion of the etching reactant vapor in the intermediate chamber to the reaction chamber, the portion being less than the entire dose, each pulse being of a first type; in a second etching mode, the control system is configured to command the first valve to close and command the second valve to open to deliver all of the dose of the etching reactant vapor in the intermediate chamber to the reaction chamber in each pulse, each pulse being of a second type different from the first type; and in a third etching mode, the control system is configured to direct the first valve to open and the second valve to open simultaneously in each pulse, wherein each pulse is of a third type different from the first type and the second type.

2. The apparatus of claim 1 , wherein the etching reactant vapor comprises a vaporized liquid or solid.

3. The device of claim 1 , further comprising a filter upstream of the intermediate chamber.

4. The apparatus of claim 1 , further comprising a heater coupled to the intermediate chamber, the heater configured to heat the intermediate chamber in a first thermal zone.

5. 5. The apparatus of claim 4, wherein the source is disposed in a second thermal zone at a second temperature, the second temperature being greater than the first temperature of the first thermal zone.

6. The apparatus of claim 1 further comprising a liquid reactant supply that delivers a liquid reactant to the supply, the supply comprising a liquid vaporizer.

7. The apparatus of claim 1, further comprising a carrier gas line that carries a carrier gas to the source of etching reactant vapor.

8. The apparatus of claim 1, wherein the control system is configured to control the partial pressure of the etching reactant vapor based at least in part on a pressure difference between a first pressure in the intermediate chamber and a second pressure in the reaction chamber.

9. 10. The apparatus of claim 1, wherein the apparatus is configured to deliver two different reactants to the reaction chamber in alternating pulses for a controlled etching process.

10. An atomic layer etching apparatus for removing a layer of material from a substrate, comprising: a reaction chamber; an intermediate chamber upstream of and in fluid communication with the reaction chamber, the intermediate chamber configured to deliver an etching reactant vapor to the reaction chamber; a source upstream of the intermediate chamber and in fluid communication with the intermediate chamber, the source configured to supply the etching reactant vapor to the intermediate chamber; a plurality of adjustable needle valves having adjustable flow conductances configured to control the flow of the etching reactant vapor into the reaction chamber; and a first valve disposed along a reactant supply line between the source and the intermediate chamber, the first valve configured to regulate the flow of the etching reactant vapor into the intermediate chamber; a second valve disposed along the reactant supply line between the intermediate chamber and the reaction chamber, the second valve configured to regulate the flow of the etching reactant vapor into the reaction chamber, the adjustable needle valve being disposed between the second valve and the reaction chamber; a control system configured to control the removal of a layer of material from a substrate by pulsing the etching reactant vapor from the intermediate chamber into the reaction chamber, the control system being configured to control a partial pressure of the etching reactant vapor based at least in part on a flow conductance of the adjustable needle valve; In a first etching mode, the control system is configured to direct the first valve to close and the second valve to open in each pulse to deliver only a portion of a dose of the etching reactant vapor in the intermediate chamber to the reaction chamber, the portion being less than the full dose, each pulse being of a first type; In a second etching mode, the control system is configured to direct the first valve to close and the second valve to open to deliver a full dose of the etching reactant vapor in the intermediate chamber to the reaction chamber in each pulse, the pulse being of a second type different from the first type.

11. The device described in claim 1, wherein the first type includes a first shape, the second type includes a second shape, and the third type includes a third shape, and the first shape, the second shape, and the third shape are different from each other.

12. The device described in claim 10, wherein the first type includes a first shape, the second type includes a second shape, and the first shape is different from the second shape.

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