Method and apparatus for filling recesses formed in a substrate surface - Patents.com

Abstract

To provide the invention relating to a method for filing one or a plurality of concave parts formed inside a front face of a base material during a manufacturing of an electron device, and a device.SOLUTION: The present invention provides a method for: providing a base material into a reaction chamber; introducing a first reaction material to the base material in a first dose amount; introducing a second reaction material to the base material in a second dose amount; remaining and introducing an initial substantial non-reaction region where the first and second reaction materials are reacted and overlapped, in which the first and second doses are overlapped, and in which the first and second regions are not overlapped; introducing a third reaction material to the base material in a third dose amount; forming and introducing a material accumulated by reacting the third reaction material with the first or the second reaction material; etching the accumulated material; and thereby filling one or a plurality of concave parts. A device for filling each concave part is disclosed.SELECTED DRAWING: Figure 2

Description

[Technical field]

[0001] The present disclosure relates generally to methods and apparatus for manufacturing electronic devices. More specifically, the present disclosure relates to methods and apparatus for filling one or more recesses formed in a surface of a substrate during the manufacture of an electronic device. [Background technology]

[0002] During the manufacture of electronic devices such as integrated circuits (ICs), recesses, such as gaps or trenches, may be created in a substrate. Filling the recesses can take a variety of forms depending on the particular application.

[0003] Typical trench fill processes can be subject to shortcomings, including void formation within the trench. Voids can form if the fill material forms a constriction near the top of the trench before the trench is completely filled. Such voids can compromise the device isolation of devices on an integrated circuit and the overall structural integrity of the IC. Unfortunately, preventing the formation of voids during trench fill can often constrain the size of the trench, which can limit the device packing density of the device.

[0004] When trenches are filled for device isolation, an important parameter in measuring the effectiveness of device isolation can be the electric field threshold voltage, i.e., the voltage required to generate a parasitic current connecting adjacent insulating devices. The electric field threshold voltage can be affected by many physical and material properties during processing, such as trench width, dielectric constant of trench fill material, substrate doping, field implant dose, and substrate bias.

[0005] Void formation can be mitigated by reducing the trench depth and / or sloping the trench sidewalls so that the trench opening is wider at the top than at the bottom of the trench. The tradeoff in reducing the trench depth is that it can reduce the effectiveness of device isolation, while the larger top opening of a trench with sloped sidewalls can use up area for other integrated circuits. These problems can become even more problematic when attempting to shrink device dimensions. Therefore, improved methods and apparatus for filling recesses may be desirable. Summary of the Invention [Means for solving the problem]

[0006] Various embodiments of the present disclosure relate to methods of filling recesses, such as trenches, in a surface of a substrate. The manner in which various embodiments of the present disclosure address the shortcomings of conventional methods are discussed in more detail below, but generally, various embodiments of the present disclosure provide improved methods and apparatus suitable for filling recesses in a substrate surface. For example, exemplary methods and apparatus can be used to seamlessly fill high aspect ratio recesses with a desired material, such as a dielectric material.

[0007] According to at least one embodiment of the present disclosure, a method of filling a recess formed in a surface of a substrate includes providing a substrate in a reaction chamber, introducing a first reactant to the substrate at a first dose onto a surface of the recess, introducing a second reactant to the substrate at a second dose onto the surface of the recess, where the first and second doses overlap in regions where they overlap and leave regions where the first and second doses do not overlap, introducing a third reactant to the substrate at a third dose, where the third reactant reacts with either the first or second reactant in regions where the first and second doses do not overlap, thereby depositing material, and etching the deposited material in the recess. According to various aspects, a concentration of the first reactant in the overlapping regions is different than a concentration of the first reactant in regions where the first and second regions do not overlap. The deposition cycles, including the steps of introducing a first reactant to the substrate, the step of introducing a second reactant to the substrate, and the step of introducing a third reactant to the substrate, can be repeated one or more times before the method proceeds to the step of etching the deposited material. Furthermore, the deposition cycles, including the one or more deposition cycles combined with the step of etching the deposited material, can be repeated several times to fill the recess. According to a further aspect, one of the first and second reactants is introduced at a saturation dose and the other of the first and second reactants is introduced at a subsaturation dose. According to a further example, during the step of etching the deposited material, the etch rate of the material can be higher in the overlapping region of the first and second regions compared to the non-overlapping region. By having the doses of the first and second reactants such that the reactants overlap at the overlapping region at the top of the recess, the first and second reactants react at the top of the recess and prevent or reduce further reaction at the top of the recess. In the initial unreacted region at the bottom of the recess where the first and second reactants do not overlap, the first or second reactant can further react with a third reactant, thereby filling the recess from the bottom upwards.

[0008] According to further embodiments, a semiconductor processing apparatus is provided for providing an improved or at least alternative method of filling recesses, such as those disclosed herein. According to at least one embodiment of the present disclosure, the semiconductor processing apparatus includes one or more reaction chambers housing a substrate including a surface having a recess formed therein, a first source for a first reactant in gas communication with one of the reaction chambers via a first valve, a second source for a second reactant in gas communication with one of the reaction chambers via a second valve, a third source for a third reactant in gas communication with one of the reaction chambers via a third valve, an etchant source in gas communication with one of the reaction chambers via a fourth valve, and an etchant source operatively connected to the first, second, third, and fourth gas valves for: introducing the first reactant to the substrate over the recesses in a first dose; and a controller configured and controlled to control: introducing a first reactant into the recess in a dose amount such that the first and second doses overlap in the overlapping regions and leave areas where the first and second regions do not overlap (e.g., where the concentration of one of the first and second doses is negligible or less than about 1% of the other of the first or second reactant and / or less than about 1% of the concentration of the same reactant in the overlapping regions); introducing a third reactant into the substrate in a third dose amount such that the third reactant reacts with the first or second reactant in the areas where the first and second regions do not overlap, thereby depositing material; and etching the deposited material in the recess. The deposition cycle including introducing the first reactant, introducing the second reactant, and introducing the third reactant may be repeated before the step of etching the deposited material, as described above. Similarly, one or more deposition cycles combined with the step of etching the deposited material may be repeated several times to fill the recess.

[0009] According to still further exemplary embodiments of the present disclosure, a semiconductor structure may be formed using the methods and / or apparatus described herein.

[0010] For purposes of summarizing the invention and the advantages achieved over the prior art, certain objects and advantages of the invention are described herein above. Of course, it should be understood that not all such objects or advantages may be achieved by any particular embodiment of the invention. Thus, those skilled in the art will recognize that the invention may be embodied or carried out in a manner that achieves or optimizes, for example, one advantage or group of advantages as taught or suggested herein, without necessarily achieving other objects or advantages as may be taught or suggested herein. These and other embodiments will be readily apparent to those skilled in the art from the following detailed description of certain embodiments, taken in conjunction with the drawings, and the invention is not limited to any particular embodiment disclosed.

[0011] A more complete understanding of the exemplary embodiments of the present disclosure can be obtained by reference to the detailed description and claims when considered in connection with the following illustrative drawings. [Brief description of the drawings]

[0012] [Figure 1] 1A illustrates a schematic diagram of a PEALD (plasma enhanced atomic layer deposition) apparatus suitable for filling features in accordance with at least one embodiment of the present disclosure, and FIG IB illustrates a schematic diagram of a precursor delivery system using an operable flow path system (FPS) in accordance with at least one embodiment of the present disclosure. [Diagram 2] FIG. 2 illustrates a flow chart of a method for filling a recess in accordance with at least one embodiment of the present disclosure. [Diagram 3] FIG. 3 illustrates a flow chart of a method for filling a recess according to another embodiment of the present disclosure. [Figure 4] FIG. 4 illustrates a structure according to another embodiment of the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] Although certain specific embodiments and examples are disclosed below, it will be understood by those skilled in the art that the invention extends beyond the specifically disclosed embodiments and / or uses of the invention, as well as obvious modifications and equivalents thereof. Therefore, it is not intended that the scope of the disclosed invention should be limited by the specific disclosed embodiments described below.

[0014] Turning now to the figures, Figure 2 shows a flow chart of a method 100 in accordance with at least one embodiment of the present disclosure. The method 100 can be used, for example, to fill one or more recesses, sometimes referred to as gaps or features, created during the fabrication of a structure. The recesses can be less than 40 or even 20 nm wide and / or greater than 40, 100, 200 or even 400 nm deep. The aspect ratio of the recesses can range, for example, from about 5:1 to about 30:1.

[0015] As shown in FIG. 2, method 100 includes providing a substrate to a reaction chamber (Step 105), introducing a first reactant to the substrate in a first dose onto the surface of the recess (Step 110), introducing a second reactant to the substrate in a second dose onto the surface of the recess (Step 120), introducing a third reactant to the substrate in a third dose, where the third reactant reacts with either the first or second reactant in areas where the first and second doses do not overlap, thereby depositing material (Step 130), and etching the deposited material in the recess (Step 140).

[0016] Step 105 includes providing a substrate to the reaction chamber. As used herein, "substrate" refers to any material having a surface onto which a material can be deposited. The substrate may include a bulk material, such as silicon (e.g., single crystal silicon), or may include one or more layers overlying a bulk material. Additionally, the substrate may include various features, recesses (e.g., trenches or vias), lines, and the like, formed in or on at least some of the layers of the substrate. As a particular example, the substrate may include layers of SiN, SiOx, and / or W, at least one of which has at least one recess formed therein.

[0017] During step 105, the substrate can be brought to a desired temperature using, for example, a substrate heater and / or radiant or other heaters. The temperature during steps 110-130 or 110-140 can be from about 100° C. to about 550° C. or from about 250° C. to about 450° C. The pressure in the reaction chamber during such steps can be from about 1 to about 9 or from about 3 to about 7 Torr.

[0018] According to various examples of the disclosure, by having doses of the first and second reactants such that the reactants overlap at the top of the recess, the first and second reactants can react at the top (overlapping area) and prevent or reduce further reaction at the top of the recess. At the bottom of the recess where the first and second reactants did not overlap (e.g., where the concentration of one of the reactants is significantly lower - e.g., less than about 1 percent of the other and / or less than about 1 percent of the concentration in the overlapping area), a reactant can still react with a third reactant to thereby deposit material.

[0019] According to embodiments of the present disclosure, a dose of one of the first and second reactants may be saturating (e.g., a relatively high amount or concentration and / or a long pulse time, etc.) such that one of said first and second reactants covers the entire or substantially entire recess, while a dose of the other of the first and second reactants may be subsaturating (e.g., a relatively short pulse time and / or a low concentration / amount, etc.) to promote the first and second reactants to overlap only in the upper (overlapping) region of the recess, or to overlap only in the substantially upper (overlapping) region. In this context, relatively low may mean about 10, 5, 2, or 1% or less of the concentration and / or pulse amount or time of one reactant compared to the other reactant, and relatively high may mean that the other reactant has a concentration and / or pulse amount or time that is about 10, 20, 50, or about 100 times greater for one reactant than the other.

[0020] The deposition cycle can include steps 110-130. The deposition cycle can be repeated multiple times to fill the recesses, as shown by loop 150. The deposition cycle may be repeated, for example, about 1-10,000 times, about 5-2,000 times, or about 10-1,000 times. Excess reactants and / or by-products can be removed after one or more (e.g., each) of steps 110-130 and / or 140 to avoid direct reactions between reactants that could cause contamination in the reaction chamber.

[0021] Method 100 may be partially repeated via loop 160, for example if the top of the recess still blocks reactants for reaction at the bottom. Also, a combination of full repetition via loop 150 and partial repetition via loop 160 may be performed. In this manner, the speed of the recess filling method may be increased.

[0022] As noted above, one of the first and second reactants may be introduced in a saturated state (e.g., a relatively large or long dose) and the other of the first and second reactants may be introduced in a subsaturated state (e.g., a relatively small or short dose). The reactant provided in the saturated dose penetrates deep into the recess and reaches the bottom of the recess, whereas the reactant provided in the subsaturated dose does not penetrate deep into the recess and remains in the region. Thus, reaction between the first and second reactants occurs only or substantially only in the upper / overlapping region of the recess, thereby inhibiting or substantially inhibiting further reaction in the upper / overlapping region.

[0023] One of the first and second reactants may be a potential growth reactant, while the other of the first and second reactants may include a low-growth reactant that results in relatively low growth in combination with the potential growth reactant. Thus, the reaction between the first reactant and the second reactant may result in relatively low growth in an upper / overlapping region of the recess, such that the upper / overlapping region may not be disturbed by deposition of material before the bottom of the recess is substantially filled.

[0024] One of the first and second reactants can be introduced to cover a corresponding one of the first and second regions that substantially covers an entire surface of the one or more recesses, and one of the first and second reactants can be a potential growth reactant that provides potential growth dependent on the other reactant.

[0025] One of the potential growth reactants, the first and second reactants, may include silicon. The first / second growth reactants may be selected from the group consisting of silane amines, siloxane amines, silazane amines (aminosilanes, aminosiloxanes, and aminosilazanes). For example, the potential growth reactant may include a silane diamine, such as N,N,N',N'-tetraethylsilane diamine, sold by Air Liquide (Paris, France) under the name ALOHA™ SAM.24.

[0026] The practical low-growth reactants are He, Ne, Ar, Kr, Xe, N2, NH 3、 and N2H4, which may optionally be activated by a plasma (directly or remotely). Nitrogen in combination with the potential growth reactants may result in relatively low growth at the top of the recess. In some cases, it may be advantageous to provide a substantially low growth reactant prior to providing the potential growth reactants.

[0027] The third reactant may include a high-growth reactant that combines with the potential growth reactant to result in relatively high growth. To ensure that the third reactant reaches the bottom of the recess, the third reactant may be introduced at a relatively high dose so that the third reactant reacts with the potential growth reactants at the bottom of the recess. Reaction at the top of the trench with the third reactant may be inhibited because the first and second reactants may already have reacted at the top of the recess.

[0028] The third reactant may include an oxidizer, such as one or more reactants selected from the group consisting of water, hydrogen peroxide, molecular oxygen, and ozone, which may also be activated by the plasma (directly or remotely). Oxygen in combination with a silane amine (e.g., a silane diamine, such as N,N,N',N'-tetraethylsilane diamine) may result in relatively high growth at the bottom of the feature. For example, N,N,N',N'-tetraethylsilane diamine, N plasma, and O plasma may be provided in a cyclically repeated reaction to deposit the material. Alternatively, N plasma, N,N,N',N'-tetraethylsilane diamine, and O plasma may be provided in a cyclically repeated reaction to deposit the material.

[0029] As shown in FIG. 2, after at least one deposition cycle (steps 110-130), a step 140 of etching the deposited material is performed. Step 140 can be configured such that the etch rate of the deposited material is higher in the top (e.g., overlapping) regions of the recesses relative to the bottom (e.g., non-overlapping) regions of the recesses. The number of repetitions of loops 150, 160 relative to loop 170 can be manipulated based on, for example, the dimensions (e.g., height, width, or aspect ratio), configuration (e.g., how densely packed the recesses are), and / or geometry (e.g., the shape of the recess openings and / or the shape of the recess walls).

[0030] According to various examples of the present disclosure, step 140 includes a dry etching process. The etchant used during step 140 may be activated, for example, by a direct or remote plasma unit. Exemplary etchants that may be used include halogens: x F y , where x and y are integers (e.g., CF4, C2F6, C3F8, or C4F8), including CHF3, NF3, SF6, Cl2, BCl3, HBr, and HI. N2, O2, Ar, He, NO x、Additional additive gases, such as SiO 2 , SiO 3 , SiO 4 , SiO 5 , SiO 6 , SiO 7 , SiO 8 , SiO 9 , SiO 2 , SiO 4 , SiO 2 , SiO 4 , SiO 5 , SiO 6 , SiO 8 , SiO 9 , SiO 2 , SiO 4 , SiO 2 ...

[0031] 3 shows a flow chart of a method 200 in accordance with at least one embodiment of the present disclosure. Method 200 is similar to method 100, except that method 200 includes step 230, in which one of the first and second reactants is again introduced to the substrate prior to the third reactant. Steps 205, 210, 220, 240, and 250 may be the same as or similar to steps 105-140 described above in connection with FIG. 2. Additionally, method 200 may include loops 260, 270 that repeat portions or all of method 200.

[0032] For example, a silicon reactant such as N,N,N',N'-tetraethylsilanediamine, a nitrogen reactant including, for example, a nitrogen plasma, and an oxygen reactant including, for example, an oxygen plasma may then be provided one or more times before proceeding to etch the deposited material. Loop 260 and / or loop 270 may be repeated, for example, about 1-10,000 times, 5-2,000 times, or 10-1,000 times. Adding step 230 to the sequence (e.g., doubling the nitrogen plasma step) better ensures that the top reactant is reacted and substantially inactivated before a third reactant (e.g., oxygen) plasma is provided.

[0033] The third reactant may include an oxidizer such as ozone and / or hydrogen peroxide, which may be combined with a silanediamine, such as N,N,N',N'-tetraethylsilanediamine, to provide high growth. The ozone and / or hydrogen peroxide do not need to be activated by a plasma to react with the silanediamine to provide relatively high growth, which is beneficial because the energy of the plasma may be lower deep within the recess.

[0034] The reactants for steps 210-250 may be the same or similar to those described above. Alternatively, the potential growth reactant may include an organometallic, such as an organoaluminum, such as trimethylaluminum (TMA). The potential growth reactant may include an organometallic, such as an organoaluminum, such as trimethylaluminum (TMA), and the substantial low-growth reactant may include ozone. Ozone in combination with trimethylaluminum can result in low-growth at the top of the recess.

[0035] The third reactant may include hydrogen peroxide, which in combination with trimethylaluminum may result in high growth at the bottom of the recess; hydrazine, which in combination with trimethylaluminum may result in high growth at the bottom of the recess; and / or water, which in combination with trimethylaluminum may result in high growth at the bottom of the recess.

[0036] 4 illustrates a structure 400 formed according to an exemplary method (e.g., method 100 or method 200) and / or using an apparatus described herein. The structure 400 includes a substrate 402, a recess 404 formed therein, and a deposited material 406. The deposited material 406 can be seamless such that no visible voids are formed in the deposited material 406.

[0037] 1A and 1B, there is illustrated a semiconductor processing apparatus 30. The semiconductor processing apparatus 30 includes one or more reaction chambers 3 housing a substrate including a surface having a recess formed therein, a first source 21 for a first reactant in gas communication with one of the reaction chambers via a first valve 31, a second source 22 for a second reactant in gas communication with one of the reaction chambers via a second valve 32, a third source 25 for a third reactant in gas communication with one of the reaction chambers via a third valve 33, an etchant source or fourth source 26 in gas communication with one of the reaction chambers via a fourth valve 34, and operatively connected to the first, second, third, and fourth gas valves. and a controller 27 configured and controlled to control: introducing a first reactant to the substrate at a first dose onto the recess, introducing a second reactant to the substrate at a second dose onto the recess, where the first and second doses overlap in areas where the first and second doses overlap and leave areas where the first and second regions do not overlap, introducing a third reactant to the substrate at a third dose, where the third reactant reacts with the first or second reactant in areas where the first and second regions do not overlap, thereby depositing material, and etching the deposited material in the recess. Although not shown, the semiconductor processing equipment 30 may include additional sources (e.g., for additives described herein, for inert gases, etc.) and additional components.

[0038] Optionally, the semiconductor processing equipment 30 includes a heater for activating the reaction by increasing the temperature of one or more of the substrate, the first, second, and third reactants, the etchant, and / or the additive. Exemplary single-wafer reactors specifically designed for carrying out ALD processes are commercially available from ASM International NV (Almere, The Netherlands) under the trade names Pulsar®, Emerald®, Dragon®, and Eagle®. Exemplary batch ALD reactors specifically designed for carrying out ALD processes are also commercially available from ASM International NV under the trade names A400™ and A412™.

[0039] Optionally, the semiconductor processing equipment 30 may include a radio frequency source operatively connected to a controller configured and arranged to generate a plasma of the first, second, or third reactant and / or etchant and / or additive. Plasma enhanced atomic layer deposition (PEALD) may be performed in an Eagle® XP8 PEALD reactor available from ASM International NV, Almere, The Netherlands, which includes a plasma source for activating one or more reactants.

[0040] A process cycle using plasma may be performed using a semiconductor processing apparatus 30, preferably in conjunction with a programmed control for performing the sequences described herein, which may be used in at least some embodiments of the present disclosure. In the apparatus shown in Fig. 1A, a pair of conductive plate electrodes 4, 2 are provided in parallel and facing each other in the interior 11 (reaction region) of a reaction chamber 3, and a plasma is excited between the electrodes by applying RF power (e.g., 13.56 MHz or 27 MHz) from a power source 20 to one side and electrically grounding the other side 12.

[0041] The lower stage 2 (lower electrode) is equipped with a temperature regulator so that the temperature of the substrate 1 placed thereon can be maintained at a relatively constant temperature. The upper electrode 4 also functions as a shower plate, and reactant gases (and optionally a noble gas), precursor gases, and etching gases are introduced into the reaction chamber 3 through gas lines 41-44, respectively, and through the shower plate 4.

[0042] Further, in the reaction chamber 3, a circular duct 13 having an exhaust line 7 is provided, through which gas in the interior 11 of the reaction chamber 3 is exhausted. Further, for example, the transfer chamber 5 arranged below the reaction chamber 3 is provided with a seal gas line 24 for introducing a seal gas into the interior 11 of the reaction chamber 3 through the interior 16 (transfer zone) of the transfer chamber 5. A separation plate 14 is provided to separate the reaction zone from the transfer zone (a gate valve through which the substrate is transferred to and from the transfer chamber 5 is omitted from this figure). The transfer chamber is also provided with an exhaust pipe 6. In some embodiments, the deposition of the multi-element film and the surface treatment are performed in the same reaction space, so that all steps can be performed consecutively without exposing the substrate to air or other oxygen-containing atmosphere. In some embodiments, for example, a remote plasma unit can be used to excite gas from one or more of the sources 21, 22, 25, and / or 26.

[0043] In some embodiments, the system shown in FIG. 1A for switching between the flow of inert gas and the flow of precursor or reactant gas as shown in FIG. 1B can be used to introduce the precursor or reactant gas in a pulsed manner without substantially fluctuating the pressure of the reaction chamber. FIG. 1B illustrates a precursor supply system using a flow path system (FPS) according to an embodiment of the present invention (black valves indicate closed valves). As shown in FIG. 1B (a), when a precursor is supplied to a reaction chamber (not shown), a carrier gas, for example, Ar (or He), first flows through a gas line having valves b and c, and enters a bottle (reservoir) 20. The carrier gas flows out of the bottle 20 carrying an amount of precursor gas according to the vapor pressure in the bottle 20, flows through a gas line having valves f and e, and is supplied to the reaction chamber together with the precursor. In this case, valves a and d are closed. When only a carrier gas (for example, a noble gas) is supplied to the reaction chamber, the carrier gas flows through a gas line having a valve while bypassing the bottle 20, as shown in FIG. 1B (b). In this case, valves b, c, d, e, and f are closed.

[0044] The precursor may be delivered using a carrier gas. In the case of ALD, since ALD is a self-limiting adsorption reaction process, the number of deposited precursor molecules may be determined by the number of reactive surface sites and is independent of the precursor exposure after saturation, and the precursor delivery is such that the reactive surface sites are saturated every cycle. The plasma for deposition may be generated in situ, for example, in a gas that flows continuously through the deposition cycle. In other embodiments, the plasma may be generated remotely and provided to the reaction chamber.

[0045] In some embodiments, a dual chamber reactor (two zones or compartments for processing substrates located close to each other) can be used, and reactant gases and noble gases can be supplied through shared lines, while precursor gases are supplied through non-shared lines.

[0046] Those skilled in the art will appreciate that the apparatus includes one or more control devices, such as controller 27, programmed or otherwise configured to carry out the deposition processes described elsewhere herein. The controller may be in communication with the various power supplies, heating systems, pumps, robotics, and gas flow controllers or valves of the reactor.

[0047] It should be understood that the configurations and / or methods described herein are exemplary in nature, and that these specific embodiments or examples are not to be construed in a limiting sense, as numerous variations are possible. The specific routines or methods described herein may represent one or more of any number of processing strategies. Thus, the various illustrated operations may be performed in the illustrated sequence, in other sequences, or may be omitted in some cases.

[0048] The subject matter of the present disclosure includes all novel and non-obvious combinations and subcombinations of the various process, system, and configurations, as well as other features, functions, operations and / or properties disclosed herein, and any and all equivalents thereof. [Explanation of symbols]

[0049] 1 Base material 2 Lower stage (lower electrode) 3. Reaction chamber 4 Upper electrode 5. Transfer chamber 6 Exhaust pipe 7 Exhaust Line 11 Inside the reaction chamber 13 Circular Duct 16 Inside the transfer chamber 20 Bottle (storage section) 21 Primary Source 22 Secondary Source 25 Third Source 26 The fourth source 27 Controller 30 Semiconductor processing equipment 31 First Valve 32 Second Valve 33 The Third Valve 34 The Fourth Valve 41~44 Gas lines 100 The method of the present invention 400 Structure 402 Base material 404 Recess 406 Material

Claims

1. 1. A method of filling a recess formed in a surface of a substrate, comprising the steps of: providing the substrate in a reaction chamber; introducing a first reactant into the substrate at a first dose onto a surface of the recess; introducing a second dose of a second reactant into the substrate onto a surface of the recess, the first and second doses overlapping at an overlapping region at a top of the recess and leaving a non-overlapping region at a bottom of the recess; introducing a third dose of a third reactant to the substrate, the third reactant reacting with the first or second reactant in areas where the first and second doses do not overlap, thereby depositing material; and e.g., etching the deposited material in the recess.

2. 10. The method of claim 1 further comprising the step of purging any unreacted first reactant.

3. 10. The method of claim 1 , wherein the steps of introducing a first reactant, introducing a second reactant, and introducing a third reactant are repeated prior to etching the material.

4. 10. The method of claim 1, wherein one of the first and second reactants is introduced at a saturating dose and the other of the first and second reactants is introduced at a subsaturating dose.

5. 2. The method of claim 1, wherein during the step of etching the material, an etch rate of the material is higher in areas where the first and second doses overlap compared to areas where the first and second doses do not overlap.

6. 10. The method of claim 1, wherein the steps of introducing a first reactant, introducing a second reactant, introducing a third reactant, and etching a material are repeated.

7. The method of claim 1 , wherein the first reactant comprises nitrogen.

8. The first reactant is He, Ne, Ar, Kr, Xe, N ２ , N.H. ３ and N ２ H ４ The method of claim 7, wherein the compound is selected from the group consisting of:

9. The method of claim 1 , wherein the second reactant comprises silicon.

10. 10. The method of claim 9, wherein the second reactant is selected from the group consisting of silane amines, siloxane amines, and silazane amines.

11. The method of claim 10 , wherein the third reactant comprises oxygen.

12. 12. The method of claim 11, wherein the third reactant is selected from the group consisting of water, hydrogen peroxide, molecular oxygen, and ozone.

13. The method of claim 1 , wherein the third dose is a saturation dose.

14. The method of claim 1 , wherein the first reactant is activated by a plasma.

15. The method of claim 1 , wherein the third reactant is plasma activated.

16. The step of etching the material comprises: ｘ F ｙ , C.H.F. ３ , N.F. ３、 Science fiction ６ , Cl ２ , BCl ３ 13. The method of claim 1, wherein the method is performed using an etchant comprising one or more of: HBr, HCl, and HI.

17. A semiconductor structure formed according to the method of claim 1.

18. 1. A semiconductor processing apparatus comprising: one or more reaction chambers for receiving a substrate including a surface having a recess formed therein; a first source for a first reactant in gas communication with one of the reaction chambers via a first valve; a second source for a second reactant in gas communication with one of the reaction chambers through a second valve; a third source for a third reactant in gas communication with one of the reaction chambers through a third valve; an etchant source in gas communication with one of the reaction chambers through a fourth valve; operatively connected to the first, second, third, and fourth gas valves; and introducing a first reactant into the substrate at a first dose onto the recess; introducing a second reactant into the substrate at a second dose onto the recess; introducing said first and second doses so that they overlap at an overlapping region at a top of said recess and leaving a non-overlapping region at a bottom of said recess; introducing a third dose of a third reactant to the substrate, the third reactant reacting with the first or second reactant in areas where the first and second doses do not overlap, thereby depositing material; and a controller configured and programmed to control etching the deposited material in the recess.

19. The etching agent is C ｘ F ｙ , C.H.F. ３ , N.F. ３、 Science fiction ６ , Cl ２ , BCl ３ 20. The semiconductor processing apparatus of claim 18, comprising one or more of: HBr, HCl, and HI.

20. The semiconductor processing apparatus of claim 18 , further comprising a remote plasma between an etchant source and the one or more reaction chambers.

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