# Patent

## Title
Intrench profile

## Abstract

A method of etching a recess in a semiconductor substrate is described. The method may include forming a dielectric liner layer in a trench of the substrate where the liner layer has a first density. The method may also include depositing a second dielectric layer at least partially in the trench on the liner layer. The second dielectric layer may initially be flowable following the deposition, and have a second density that is less than the first density of the liner. The method may further include exposing the substrate to a dry etchant, where the etchant removes a portion of the first liner layer and the second dielectric layer to form a recess, where the dry etchant includes a fluorine-containing compound and molecular hydrogen, and where the etch rate ratio for removing the first dielectric liner layer to removing the second dielectric layer is about 1:1.2 to about 1:1.

## Background
CROSS-REFERENCES TO RELATED APPLICATIONS
This application is a Divisional of U.S. patent application Ser. No. 13/624,724, filed Sep. 21, 2012, which claims the benefit of U.S. Provisional Application No. 61/539,279, filed Sep. 26, 2011, entitled “Improved Intrench Profile,” the entire disclosures of both of which are hereby incorporated by reference for all purposes.


BACKGROUND
Semiconductor processing often include many distinct manufacturing steps. With the current state of technology, circuit components are routinely formed on nanometer scales, and sensitive manufacturing techniques are required. For instance, with integration schemes for shallow-trench-isolation (“STI”) gate formation, a sacrificial film must be removed preferentially in the presence of a selective material in a nanometer thin trench. As semiconductor technology continues to evolve, these semiconductor substrate trenches continue to shrink in width, which makes film removal even more difficult.
These small width trenches create a need for delicate etching techniques. Although a variety of etch techniques are available, few provide the selective removal necessary for such intricate detail. For example, wet removal using hydrogen-fluoride solutions can be used for a selective removal. However, such a wet removal cannot be used for STI recessing because the process chemistry and bath life often cannot be sufficiently controlled for such detailed etching.
Dry etching techniques are available and have been shown to provide selective removal. For example, SiconiTM processes that use a combination of dry etchant gases including ammonia and a fluorine-containing gas have been used for better control of the material removal during the removal. However, the dry etchant gas still selectivity etches oxides of different quality at different rates. Although this oxide selectivity is often acceptable during semiconductor processing, in STI recessing, the minute selectivity can cause concave profiles in the STI trenches where a liner oxide is present with a flowable oxide. This slight concavity, or meniscus, can potentially cause integration issues with integrated passive device scaling and control gate polysilicon fill between the trenches. Thus, there is a need for improved intrench profiles in STI recess production. These and other needs are addressed by the present invention.
BRIEF SUMMARY
The present technology provides methods of removing dielectric materials of different qualities from within a trench that has been etched on a semiconductor substrate. The removal may be performed with dry etchant gases that are insensitive to the quality of a deposited oxide. By being insensitive, the dry etchant gases may remove different oxides at substantially similar rates. In this way, trenches that include multiple oxides of different qualities may be etched so that the profile within the trench is uniform across the different oxides.
Methods of etching recesses in semiconductor substrates are described. The methods may include forming a dielectric liner layer in a trench of the substrate where the liner layer has a first density. The method may also include depositing a second dielectric layer at least partially in the trench on the liner layer. The second dielectric layer may initially be flowable following the deposition, and the second dielectric layer may have a second density that is less than the first density of the liner layer. The method may further include exposing the substrate to a dry etchant, where the etchant removes a portion of the first liner layer and the second dielectric layer to form a recess, where the dry etchant includes a fluorine-containing compound and molecular hydrogen. The etch rate ratio for removing the first dielectric liner layer to removing the second dielectric layer is about 1:1.2 to about 1:1.
Embodiments of the invention also include methods of etching a dielectric material located between sections of a selective material over a semiconductor substrate. Selective materials may include materials such as polysilicon or other materials used to form structures such as floating gates. Selective materials such as polysilicon may require removal techniques that can maintain as much of the selective material as possible while removing other materials. In another sense, selective materials may be preferentially removed during certain types of wet or corrosive etching as opposed to sacrificial materials, and thus removal techniques that maintain the selective materials may be used. The methods include depositing a selective material over a semiconductor substrate. The methods may also include etching at least one trench in the selective material and semiconductor substrate that creates at least two sections of the selective material that are isolated from one another on the semiconductor substrate. The dielectric material may be deposited to at least partially fill the trench between the isolated sections of the selective material. The substrate may then be exposed to a dry etchant gas that removes a portion of the dielectric layer between the isolated sections of the selective material to form a recess. The dry etchant gas may include a fluorine-containing compound and molecular hydrogen.
Additional embodiments and features are set forth in part in the description that follows, and will become apparent to those skilled in the art upon examination of the specification and/or may be learned by the practice of the disclosed embodiments. The features and advantages of the disclosed embodiments may be realized and attained by means of the instrumentalities, combinations, and methods described in the specification.



BRIEF DESCRIPTION OF THE DRAWINGS
A further understanding of the nature and advantages of the disclosed embodiments may be realized by reference to the remaining portions of the specification and the drawings.
FIG. 1 shows a flowchart of an etch process according to disclosed embodiments.
FIG. 2 shows a flowchart of an etch process according to disclosed embodiments.
FIG. 3A shows a cross-sectional view of a substrate on which an etch process according to the present methods has been performed.
FIG. 3B shows a cross-sectional view of a substrate on which an etch process according to the present methods has been performed.
FIG. 4A shows a TEM image of a substrate on which an etch utilizing an ammonia has been performed.
FIG. 4B shows a TEM image of a substrate on which an etch process according to the present methods has been performed.



In the appended figures, similar components and/or features may have the same numerical reference label. Further, various components of the same type may be distinguished by following the reference label by a letter that distinguishes among the similar components and/or features. If only the first numerical reference label is used in the specification, the description is applicable to any one of the similar components and/or features having the same first numerical reference label irrespective of the letter suffix.
DETAILED DESCRIPTION
In the following description, for the purposes of explanation, numerous details are set forth in order to provide an understanding of various embodiments of the present invention. It will be apparent to one skilled in the art, however, that certain embodiments can be practiced without some of these details, or with additional details.
The present technology provides methods of etching recesses in semiconductor substrates in which a dry etchant that is substantially free of ammonia is used. By including a minimal concentration of ammonia, the amount of fluorine radicals within the etchant gas may be enhanced, which may allow for removal that is less sensitive to oxide quality. The dry etchant may include a fluorine-containing gas and molecular hydrogen.
Methods of etching a recess in a semiconductor substrate are described. The methods may include forming a dielectric liner layer in a trench of the substrate where the liner layer has a first density. The methods may also include depositing a second dielectric layer at least partially in the trench on the liner layer. The second dielectric layer may be initially flowable following the deposition, and the second dielectric layer may have a second density that is less than the first density of the liner layer. The methods may further include exposing the substrate to a dry etchant, where the etchant removes a portion of the first liner layer and the second dielectric layer to form a recess, where the dry etchant includes a fluorine-containing compound and molecular hydrogen, and where the etch rate ratio for removing the first dielectric liner layer to removing the second dielectric layer is about 1:1.2 to about 1:1.
Referring to FIG. 1, which shows an etch process 100 according to disclosed embodiments, a dielectric liner layer 110 may be formed on a semiconductor substrate. The dielectric liner layer initially deposited in the trench may be deposited so as to produce a substantially conformal liner. Conformality refers to a deposited film layer having a uniform thickness on both horizontal and vertical surfaces, or a step coverage equal to about one. The liner may also be formed over other layers of the substrate including pad oxides and floating gates. This liner helps to avoid shorting in the silicon through the lower quality flowable dielectrics that may be used for filling the gap due to their better gap-filling qualities such as flowability. In some embodiments, the dielectric liner layer is deposited by a less-flowable or non-flowable deposition technique, which may be HDP-CVD, or in other embodiments may be SACVD such as HARP, or PECVD such as plasma-enhanced TEOS and oxygen or TEOS and ozone. The deposited dielectric may include a silicon oxide such as an undoped silica glass or a doped silica such as phosphorous silicate glass, borosilicate glass, or borophosphosilicate glass. Still other dielectrics may include silicon nitride and silicon oxy-nitride.
An HDP deposition produces a liner layer with an HDP quality oxide, such as silicon oxide, which as the first dielectric layer has a first density as well as an overall quality that is higher than an oxide that is deposited by a flowable process. The HDP film is produced by exciting the reactant gases at low pressure or even vacuum, often with radio frequency energy, which creates a plasma near the substrate surface. The plasma energy causes the elements to be highly reactive and produces high density and high quality films. In other embodiments a thermal process may be performed on the substrate to produce the liner oxide layer in which chemical reactions of the reactant gases are caused by heating the substrate up to a high temperature to induce the reaction and formation of the film.
A second dielectric layer may be deposited 115 that is produced by a flowable deposition method, which can include spin-on-glass or flowable CVD for example. In some embodiments, flowable CVD is used to cover the dielectric liner layer and fill the trench in the substrate. The flowable oxide may be formed by exciting precursor gases separately, and then allowing them to combine in a region of the process chamber directly over the substrate to produce the flowable oxide that starts at the top of the trench, and then flows down to fill it in without creating voids or seams. The second dielectric layer has a second density that is less than the first density of the liner layer. In addition to filling the trench, in some embodiments the flowable oxide can additionally fill between pad oxide layers such as silicon nitride, or additionally can fill between polysilicon floating gates for situations including producing Nand flash, for example.
A variety of methods can be used to deposit dielectric layers that are initially flowable after deposition. For example, a flowable CVD process may be used in which a silicon precursor is introduced to the substrate processing region housing the substrate. Another precursor is introduced only after passing through a remote plasma region to create a radical precursor, such as a nitrogen precursor, which is then flowed into the substrate processing region and combined with the silicon precursor. In this technique, the silicon-containing precursor is not directly excited by an application of plasma power in the substrate processing region. Instead, plasma power just excites the precursor outside the substrate processing region. This arrangement results in the flowable deposition of a silicon-and-nitrogen-containing layer into the lined trench. The flowability of the film attenuates as the deposition proceeds and the flowability is essentially removed during a curing operation described below.
The silicon-containing precursor may contain carbon and/or nitrogen in order to ensure flowability during gapfill dielectric layer formation. In some embodiments, the silicon-containing precursor may be a carbon-free silicon-containing precursor which enables the gapfill layer to undergo less shrinkage during the curing process. The carbon-free silicon precursor may be, for example, a silicon-and-nitrogen precursor, a silicon-and-hydrogen precursor, or a silicon-nitrogen-and-hydrogen containing precursor, among other classes of silicon precursors. Specific examples of these precursors may include silyl-amines such as H2N(SiH3), HN(SiH3)2, and N(SiH3)3, among other silyl-amines. These silyl-amines may be mixed with additional gases that may act as carrier gases, reactive gases, or both. Examples of the these additional gases may include H2, N2, NH3, He, and Ar, among other gases. Examples of carbon-free silicon precursors may also include silane (SiH4) either alone or mixed with other silicon (e.g., N(SiH3)3), hydrogen (e.g., H2), and/or nitrogen (e.g., N2, NH3) containing gases. The silicon-containing precursors may also include silicon compounds that have no carbon or nitrogen, such as silane, disilane, etc. If the deposited oxide film is a doped oxide film, dopant precursors may also be used such as TEB, TMB, B2H6, TEPO, PH3, P2H6, and TMP, among other boron and phosphorous dopants.
Nitrogen may be included in either or both of the radical precursor and the silicon-containing precursor. When nitrogen is present in the radical precursor, it may be referred to as a radical-nitrogen precursor. The radical-nitrogen precursor includes plasma effluents created by exciting a more stable nitrogen-containing precursor in a plasma. For example, a relatively stable nitrogen-containing precursor containing NH3 and/or hydrazine (N2H4) may be activated in a chamber plasma region or a remote plasma system (RPS) outside the processing chamber to form the radical-nitrogen precursor, which is then transported into a plasma-free substrate processing region. The stable nitrogen precursor may also be a mixture comprising NH3 & N2, NH3 & H2, NH3 & N2 & H2 and N2 & H2, in different embodiments. Hydrazine may also be used in place of or in combination with NH3 in the mixtures with N2 and H2. The flow rate of the stable nitrogen precursor may be greater than or about 200 sccm, greater than or about 300 sccm, greater than or about 500 sccm or greater than or about 700 sccm in different embodiments. Nitrogen-containing precursors may also include N2O, NO, NO2 and NH4OH.
The radical-nitrogen precursor produced may include one or more of •N, •NH, •NH2, etc., and may also be accompanied by ionized species formed in the plasma. In other embodiments, the radical-nitrogen precursor is generated in a section of the processing chamber partitioned from the substrate processing region where the precursors mix and react to deposit the silicon-and-nitrogen layer on a deposition substrate (e.g., a semiconductor wafer). The partition may be incorporated into a showerhead that supplies the reactants to the substrate processing region. The radical-nitrogen precursor may also be accompanied by a carrier gas such as argon, helium, etc. Oxygen may be simultaneously delivered into the remote plasma region (in the form of O2 and/or O3) to adjust the amount of oxygen content in the radical-nitrogen precursor and liner or gapfill layer deposited with this technique.
The flowability may be due, at least in part, to a significant hydrogen component in the deposited film. For example the deposited film may have a silazane-type, Si—NH—Si backbone (i.e., a Si—N—H film). Flowability may also result from short chained polymers of the silazane type. The nitrogen which allows the formation of short chained polymers and flowability may originate from either the radical precursor or the silicon-containing precursor. When both the silicon precursor and the radical-nitrogen precursor are carbon-free, the deposited silicon-and-nitrogen-containing film is also substantially carbon-free. Of course, “carbon-free” does not necessarily mean the film lacks even trace amounts of carbon. Carbon contaminants may be present in the precursor materials that find their way into the deposited silicon-and-nitrogen-containing film. The amount of these carbon impurities however are much less than would be found in a silicon precursor having a carbon moiety (e.g., TEOS, TMDSO, etc.).
In other embodiments, the first and second dielectric layers are both flowable or may both not be flowable. In some embodiments the dielectrics are deposited by different mechanisms (e.g., the first is not flowable, and the second is flowable), but have similar dielectric qualities depending on the reactants used. In still other embodiments, the first and second dielectrics are deposited by the same mechanism, but have different qualities due to the use of different reactant species for the two dielectrics.
Flowable film growth may proceed while the substrate temperature is maintained at a relatively low temperature during deposition of the silicon-containing films. The flowable oxide film may be deposited on the substrate surface at a low temperature that is maintained by cooling the substrate during the deposition. The pedestal may include heating and/or cooling conduits that set the temperature of the pedestal and substrate between about −40° C. and about 1000° C., between about 100° C. and about 600° C., less than about 500° C. or at about 400° C. or less in different embodiments.
After the flowable dielectric has been deposited on the substrate, an etching process can be performed in order to remove excess dielectric in preparation for subsequent integrated passive device manufacturing steps. In some embodiments, a dry etchant gas is used to etch 120 the dielectric layers. The etchant removes a portion of both the first liner layer and the second dielectric layer. The gases included in the etchant may include gases that pass through a remote plasma region to be excited prior to entering the semiconductor processing region. The etchant may include a fluorine-containing compound and molecular hydrogen, and reacts with the dielectric layers to produce solid byproducts that sublimate when the temperature of the substrate is raised above the sublimation temperature, thereby removing the excess dielectric. The etch rate ratio for removing the first dielectric liner layer to removing the second dielectric layer may be about 1:2, or in other embodiments may be about 1:1.5, 1:1.3, 1:1.2, 1:1.1, or about 1:1. When the etch rate ratio is equal to 1:1 the separate dielectrics are removed at the same rate.
In some embodiments the dry etchant gas contains nitrogen trifluoride along with molecular hydrogen. In other embodiments the dry etchant gas is substantially free of ammonia. The dry etchant gas combination of nitrogen trifluoride and hydrogen may produce a slower reaction that is less selective of oxide quality than a dry etchant gas that includes ammonia. The addition of ammonia may reduce the concentration of fluorine in the reactive species producing ammonium fluoride and ammonium hydrogen fluoride. These products may remove a lower density and lower quality flowable dielectric at a faster rate than the higher density, higher quality liner oxide layer deposited by, for example, HDP. By having a selectivity with respect to HDP oxide that is closer to 1:1, the dry etchant gas that is substantially free of ammonia is able to produce recesses that have a less concave corner profile than a dry etchant gas that includes ammonia. In some embodiments, the dry etchant gas that is substantially free of ammonia produces a corner profile that is substantially flat against the sidewall of the recess.
The flowable dielectric may be cured following deposition in order to improve the dielectric film quality. Curing may be carried out in oxidative environments like steam, inert environments such as nitrogen, or other environments in various embodiments. The flowability of the film attenuates as the deposition proceeds and the flowability is essentially removed during a curing operation. The curing operation may involve converting the silicon-and-nitrogen-containing layer to silicon oxide. Curing involves raising the patterned substrate temperature and exposing the gapfill dielectric layer to an oxygen-containing environment. In some embodiments, the elevated temperature induces the oxide to diffuse from the liner layer into the gapfill layer which provides an additional source of oxygen from underneath the gapfill dielectric layer. The curing may be an anneal, and may be performed at temperatures below about 1000° C. In other embodiments, the curing may occur below about 800° C., 600° C., 500° C., 400° C., 300° C., or below about 200° C. Utilizing a flowable dielectric may reduce the thermal budget of the manufacturing processes, and in some cases the processes may be performed below about 600° C., 500° C., 400° C., 300° C., 200° C., or below about 100° C. in order to maintain the flowable dielectric.
Referring now to FIG. 2, a method 200 of etching a dielectric material located between sections of a selective material over a semiconductor substrate is described. The method includes depositing 210 a selective material over a semiconductor substrate. The selective material may be any material desired to be maintained while a separate material is removed. For example, and without intending to limit the invention, the selective material may be a polysilicon used as a floating gate in a flash memory cell. Another material, such as a dielectric, may be co-located on a substrate along with the selective polysilicon. The intention in some embodiments may be to remove the dielectric material while maintaining the selective polysilicon. In such a case, the dielectric may be removed in a way that limits the removal or does not remove the polysilicon. This may be performed with particular etching techniques that preferentially remove the dielectric. For example, utilizing dry etchant gases that react with oxides or nitrides but not with the polysilicon provides a way of removing the dielectic while maintaining the selective material. In other embodiments, the selective material is silicon, a deposited metal, a dielectric, or any other material that my be deposited on a substrate in which the intention is to remove significantly less of the selective material during the removal of a separate material.
After the selective material has been deposited, trenches may be etched 215 through the selective material and in some instances the semiconductor substrate. The etching creates isolated sections of the selective material located over the semiconductor substrate that are separated by the etched trenches. The trenches may display high aspect ratios in which the depth of the trench may be significantly greater than its width. Exemplary trenches may have an aspect ratio of about 2:1 or more, about 3:1 or more, about 5:1, about 7:1 or about 10:1 or more, etc.
The methods may further include depositing 220 a dielectric material within the trench. The deposition may include filling the trench completely and depositing sufficient dielectric to cover the selective material, or in other embodiments the deposition may fill the trench partially. The dielectric may be deposited past the level of the substrate so that it at least partially fills between the isolated sections of the selective material. Depending on the characteristics of the trenches, the dielectric material may be deposited by a flowable, or non-flowable method. In some embodiments with narrow and deep trenches, the dielectric may be deposited in a flowable manner in order to limit the likelihood of developing voids. In other embodiments, a higher quality dielectric may be used for improved insulation between the field components. In some embodiments spin-on-glass is used to deposit the dielectric material. In alternative embodiments the dielectric is deposited by a flowable CVD.
In some embodiments multiple dielectric depositions may be performed in order to fill the trench. For example, a liner layer may be deposited within the trenches prior to the trenches being filled with a flowable dielectric. Such a combination may provide the benefits of improved insulation from the liner layer, as well as the improved fill characteristics of a flowable dielectric. Additional examples include depositing the dielectric in a series of steps that include both deposition and etch-back of the dielectric in order to minimize bread-loafing and void formation. An initial layer of dielectric may be deposited in the trench followed by an intermediate etch process to remove dielectric buildup along the top of the trench. After the etching, the remainder of the trench may be filled with a subsequent deposition of dielectric material.
An etching process 225 may be performed after the deposition of the dielectric layer. The etching may include exposing the substrate to a dry etchant gas that removes a portion of the dielectric layer between the isolated sections of the selective material to form a recess. The dry etchant gas may be a mixture of gases that includes a fluorine-containing compound as well as molecular hydrogen. The gases may be flowed separately into the processing chamber in which the substrate resides, and in some embodiments the dry etchant gas is excited by a remote plasma source prior to its being flowed into the process chamber. In some embodiments the dry etchant gas is substantially free of ammonia, which may provide a slower reaction with a higher quantity of fluorine radicals available for reaction. The use of a dry etchant gas that is substantially free of ammonia may produce a recess with a substantially flat corner profile due to the prevented reduction of fluorine radicals into products including ammonium fluoride and ammonium hydrogen fluoride. The dry etchant gas may be completely free of ammonia in order to further prevent the removal of fluorine radicals by the formation of intermediate chemicals including ammonium fluoride and ammonium hydrogen fluoride.
In some depositions the dielectric layers are deposited well above the level of the selective material and an intermediate dielectric removal can be performed. Processes such as chemical mechanical polishing may be utilized to remove excess dielectric. The selective material may be used as the etch stop layer, which may be, for example, a field gate polysilicon or silicon nitride. Once the dielectric has been removed down to the layer of the selective material, the dry etchant may be used to remove the dielectric located between the sections of selective material.
The dielectric located between the sections of selective material may be removed based on the effective field height of the selective material. For example, the dielectric may be etched between about 200 and about 1200 angstrom. Additional examples may have the dielectric etched between about 400 and about 1000 angstrom, between about 600 and about 800 angstrom, etc. Where there are multiple sections of selective material, and multiple regions in between these sections in which dielectric must be removed, the dry etchant gas may provide recesses with cell to cell variation of less than about 10 nm. Exemplary effective field height variation between recess depths intercell is less than about 8 nm, or less than about 6 nm. The dry etchant gas may provide an etch uniformity between cells where deviations between cell recess depth and shape are less than 5%. Differences between cell depth and shape may be less than about 3%, about 2%, about 1.5%, about 1%, about 0.5%, about 0.1%, etc.
The resulting profile of the recess after the dielectric has been removed from between the sections of selective material may have a floor that is defined by the remaining dielectric material in the shallow trench isolation of the substrate. The floor profile may be substantially flat across the dielectric up to the location of where the dielectric material intersects the selective material. This point of intersection may define a corner of the recess, and the corner profile of the dielectric material may be at about a right angle with the selective material. When a right angle is formed between the dielectric material floor and the selective material wall defining the recess, a flat corner profile has been formed. An angle greater than or less than 90° may be formed, in which case the corner profile may be substantially flat. The dielectric may not be completely removed in the corners producing a slight concavity of the dielectric at the recess corner. Although the concavity may not define a perfectly circular cross section, the radius of curvature with the recess sides and floor may be less than about 5 nm. The radius of curvature may be less than about 3 nm, 2 nm, 1 nm, 5 angstrom, 3 angstrom, 2 angstrom, or about 1 angstrom in some embodiments providing a substantially flat corner profile.
The dielectric may be cured following deposition and prior to etching in order to improve the dielectric film quality. Curing may be carried out by any of the previously discussed methods. The curing may be an anneal, and may be performed at temperatures below about 1000° C. For example, the curing may occur below about 800° C., 600° C., 500° C., 400° C., 300° C., or below about 200° C. Utilizing a flowable dielectric may reduce the thermal budget of the manufacturing processes, and in some cases the processes may be performed below about 600° C., 500° C., 400° C., 300° C., 200° C., or below about 100° C. in order to maintain the flowable dielectric.
In some embodiments an oxide layer known as a tunnel oxide is deposited between the semiconductor substrate and the selective material to ensure isolation of floating gates. The tunnel oxide is deposited prior to the initial deposition of the selective material and trench formation. The dielectric deposited in the trenches and between the sections of the selective material may be etched down to the level of the tunnel oxide. Alternatively, the dielectric material may be etched between the sections of selective material, but is not etched down to the level of the tunnel oxide.
After the dielectric material has been etched from between the sections of the selective material, subsequent manufacturing may occur. An isolation layer may be deposited over the selective layer and in the etched recesses. This isolation layer may provide a liner between, for example, the floating gates and the control gate that can be subsequently deposited. A deposit of another material, such as a metal, dielectric, or some other material may be deposited after the isolation layer has been laid down. The subsequent material may be polysilicon that acts as a control gate in a flash memory cell such as a Nand flash device. A substantially flat corner profile of the etched dielectric recess may enable subsequent integrated passive device layers to be filled inside the trenches that can be a few nanometers in width, for example. When an isolation layer and a subsequent control gate layer are deposited within a recess that has a substantially flat corner profile and/or better cell uniformity, further integration issues may be prevented by providing improved interfaces for IPD scaling.
Turning now to FIG. 3A, a cross-sectional view is shown of a substrate 310 on which an etch process according to the present methods has been performed. Tunnel oxide 320 is deposited between substrate 310 and selective material 325. The selective material 325 may be a metal, a dielectric or oxide, or some other material. Selective material 325 may be polysilicon that is doped or undoped in some embodiments. Trenches 315 are created in the layers and filled with a dielectric material 319. The dielectric material may be flowable initially after deposition, and may be cured subsequent to deposition. The dielectric may then be etched back forming recess cells 330 with corners 335. The etching process may use a dry etchant gas mixture of a fluorine-containing gas and molecular hydrogen, and the dry etchant gas may be substantially free of ammonia. While corners 335 show a slight concavity, other embodiments may have them substantially flat or flat at the interface between the dielectric floor and selective material walls defining the recess cells 330 creating a right angle intersection. The cross-sectional view of FIG. 3A may be an intermediate step in processing a semiconductor device that will include deposition of a subsequent layer of material, such as polysilicon, within the recess cells formed. This subsequent material may be deposited after forming an isolation or liner layer over the selective material and within the recesses. The dielectric layer 319 may include both a liner layer as well as an additional layer of gapfill dielectric.
In FIG. 3B, a cross-sectional view is shown of a substrate 310 on which an etch process according to the present methods has been performed. The substrate 310 has a pad layer 340 deposited prior to forming the trenches 315. After trench formation, a dielectric liner material 317 may be deposited. The liner 317 may be deposited by, for example, an HDP deposition. Subsequently, a dielectric material 319 is deposited over the liner layer 317 within the trench 315. The dielectric material 319 may be initially flowable after deposition, and may be cured subsequent to deposition. The dielectric material 319 may be the same or a different quality and/or density of the dielectric liner layer 317. For example, the liner layer 317 may be of a higher quality than the dielectric material 319.
The dielectric 319 may extend above the pad oxide 340 and may be initially removed down to the layer of the pad oxide with a process such as chemical mechanical polishing. An etching process can be performed in which a dry etchant gas mixture is used to remove the dielectric material 319 and dielectric liner layer 317. The dry etchant gas mixture may include a fluorine-containing gas and molecular hydrogen, and may be substantially free of ammonia, or completely free of ammonia. The dry etchant gas removes the dielectric material 319 and liner layer 317 to produce a recess 330 that includes a corner 335. The corner 335 profile may be substantially flat indicating that the dielectric material 319 and dielectric liner 317 are removed to substantially the same depth. Removal to equivalent depth indicates that the dry etchant gas are substantially insensitive to oxide quality.
EXAMPLES
Comparative examples were made between etch selectivity using an etchant gas mixture with and without ammonia. The etches were conducted on a trench that was first lined with an HDP liner layer and then filled with a flowable oxide. The dielectrics were exposed to dry etchant gas mixtures containing nitrogen trifluoride and molecular hydrogen. In one example, the dry etchant gas also contained ammonia, while in a comparative example the dry etchant gas was substantially free of ammonia. As can be seen in Table I below, the dry etchant gas containing ammonia removes more of the flowable oxide in comparison to an HDP oxide than does the dry etchant gas that is substantially free of ammonia:







TABLE I







ETCH DEPTH OF DRY ETCHANT GAS











HDP Oxide
Flowable Oxide
Selectivity of Etching



Etch
Etch 
of Flowable Oxide



Depth 
Depth 
with respect to HDP



(angstrom)
(angstrom)
oxide













Dry Etchant Gas
114
134
1.19


Containing Ammonia





Dry Etchant Gas
114
123
1.09


Substantially Free of





Ammonia









FIGS. 4A and 4B show comparative TEM images of substrates after an etching has been performed. FIG. 4A shows a substrate on which an etch utilizing an ammonia has been performed. The corner profile as seen in the image shows a concavity indicating that the dielectric was not uniformly removed within the trench. FIG. 4B, however, shows a substrate on which an etch was performed with dry etchant gases that were substantially free of ammonia. As can be seen in the image, the corner profile is substantially flat where the dielectric layer intersects the nitride pad, creating an almost right angle corner profile. The flat corner profile indicates that the dielectric was uniformly removed within the trench.
Having disclosed several embodiments, it will be recognized by those of skill in the art that various modifications, alternative constructions, and equivalents may be used without departing from the spirit of the disclosed embodiments. Additionally, a number of well known processes and elements have not been described in order to avoid unnecessarily obscuring the present invention. Accordingly, the above description should not be taken as limiting the scope of the invention.
It is noted that individual embodiments may be described as a process which is depicted as a flowchart, a flow diagram, or a block diagram. Although a flowchart may describe the method as a sequential process, many of the operations can be performed in parallel or concurrently. In addition, the order of the operations may be rearranged. A process may be terminated when its operations are completed, but could have additional steps not discussed or included in a figure. Furthermore, not all operations in any particularly described process may occur in all embodiments. A process may correspond to a method, a function, a procedure, a subroutine, a subprogram, etc. When a process corresponds to a function, its termination corresponds to a return of the function to the calling function or the main function.
Where a range of values is provided, it is understood that each intervening value, to the smallest fraction of the unit of the lower limit, unless the context clearly dictates otherwise, between the upper and lower limits of that range is also specifically disclosed. Each smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in that stated range is encompassed. The upper and lower limits of those smaller ranges may independently be included or excluded in the range, and each range where either, neither, or both limits are included in the smaller ranges is also encompassed within the invention, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included.
As used herein and in the appended claims, the singular forms “a”, “an”, and “the” include plural references unless the context clearly dictates otherwise. Thus, for example, reference to “a dielectric material” includes a plurality of such materials, and reference to “the application” includes reference to one or more applications and equivalents thereof known to those skilled in the art, and so forth.
Also, the words “comprise”, “comprising”, “include”, “including”, and “includes”, when used in this specification and in the following claims, are intended to specify the presence of stated features, integers, components, or steps, but they do not preclude the presence or addition of one or more other features, integers, components, steps, acts, or groups.

## Claims

1. A method of etching a recess in a semiconductor substrate, the method comprising:
forming a dielectric liner layer in a trench of the substrate, wherein the liner layer has a first density;
depositing a second dielectric layer at least partially in the trench on the liner layer, wherein the second dielectric layer is initially flowable following the deposition, and wherein the second dielectric layer has a second density that is less than the first density of the liner layer;
exposing the substrate to dry etchant, wherein the etchant removes a portion of the first liner layer and the second dielectric layer to form a recess, wherein the dry etchant comprises a fluorine-containing compound and molecular hydrogen, and wherein an etch rate ratio for removing the first dielectric liner layer to removing the second dielectric layer is about 1:1.2 to about 1:1.

2. The method of claim 1, wherein the first dielectric liner layer comprises a high-density plasma formed silicon oxide layer.

3. The method of claim 1, wherein the second dielectric layer comprises a silicon oxide layer deposited by FCVD.

4. The method of claim 1, wherein the fluorine-containing compound comprises NF3.

5. The method of claim 1, wherein the dry etchant is substantially free of ammonia.

6. The method of claim 1, wherein the recess has a substantially flat corner profile.

7. The method of claim 1, further comprising curing the second dielectric layer after it is deposited.

8. The method of claim 1, wherein the dielectric layers are deposited and etched at a temperature of about 400° C. or less.

9. A method of etching a recess in a semiconductor substrate located in a semiconductor processing chamber, the method comprising:
forming a dielectric liner layer in a trench of the substrate, wherein the liner layer has a first density;
depositing a second dielectric layer at least partially in the trench on the liner layer, wherein the second dielectric layer is initially flowable following the deposition, and wherein the second dielectric layer has a second density that is less than the first density of the liner layer;
flowing a dry etchant through a showerhead positioned within the semiconductor processing chamber; and
exposing the substrate to the dry etchant, wherein the etchant removes a portion of the first liner layer and the second dielectric layer to form a recess, wherein the dry etchant comprises a fluorine-containing compound and molecular hydrogen, and wherein an etch rate ratio for removing the first dielectric liner layer to removing the second dielectric layer is about 1:1.2 to about 1:1.

10. The method of claim 9, wherein the first dielectric liner layer comprises a high-density plasma formed silicon oxide layer.

11. The method of claim 9, wherein the second dielectric layer comprises a silicon oxide layer deposited by FCVD.

12. The method of claim 9, wherein the fluorine-containing compound comprises NF3.

13. The method of claim 9, wherein the dry etchant is substantially free of ammonia.

14. The method of claim 9, wherein the recess has a substantially flat corner profile.

15. The method of claim 9, further comprising curing the second dielectric layer after it is deposited.

16. The method of claim 9, wherein the dielectric layers are deposited and etched at a temperature of about 400° C. or less.