DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

[0037] Though described in the context of certain preferred materials, it will be understood, in view of the disclosure herein, that the described methods and structures will have application to a variety of other materials suitable for capacitor dielectrics over rugged surfaces. Moreover, while illustrated for memory cell storage capacitors, the skilled artisan will readily appreciate application of the described methods to other roughened electrodes, such as the floating gate electrode of an Electrically Erasable Programmable Read Only Memory (EEPROM) device.

[0038] As discussed in the Background section above, coating capacitor electrodes, and particularly electrode structures bearing hemispherical grain (HSG) silicon, by conventional chemical vapor deposition (CVD) produces less than perfect conformality. While much research has been devoted to obtaining more conformal step coverage of semiconductor stepped features in general, it is very difficult to supply the same concentration of depositing species to all surfaces of such structures. In particular, it is difficult to supply the same concentration of depositing species at the upper surfaces of HSG grains as supplied to neck regions between grains. This problem is particularly exacerbated where the textured electrode conforms to a three-dimensional folding structure, such as the stacked and trench designs of FIGS. 1A to 2 , and even more so for structures with interior volumes like that of FIG. 1B . Accordingly, full advantage of the increased surface area of the HSG silicon is not realized.

[0039] By providing almost perfect step coverage, the preferred embodiments advantageously obtain the minimum necessary thickness for the desired capacitor dielectric layers over all surfaces of HSG grains. Desirably, the methods of the preferred embodiment are less dependent upon the relative concentration of reactant species over grains as compared to confined grain intersections.

[0040] Moreover, the preferred embodiments provide methods of depositing high k materials in a manner that enables integration with high-surface area textured surfaces and with silicon electrodes, which is most often employed to produce microstructural roughness such as an HSG morphology. Rather than presenting a choice between high surface area textures over three-dimensional folding structures and high k dielectrics, the preferred embodiments allow the use of both techniques to achieve very high capacitance/footprint in a repeatable, production-worthy process.

[0041] The preferred embodiments provide exemplary processes for depositing Al 2 O 3 (k ≈10), ZrO 2 (k≈12-20), TiO 2 (k≈20-50), mixed zirconium silicon oxide (k≈8-13), and nanolaminate dielectrics formed by combinations of the above. Similarly, methods are provided for depositing electrode materials over the dielectric and HSG silicon. These materials are all formed by methods compatible with HSG silicon, furthermore producing almost perfect conformality. Thus, the preferred embodiments allow increased capacitance not only due to the high k dielectric materials, but also due to taking full advantage of the increased surface area afforded by HSG silicon. Such conformality obtains even over high aspect ratio structures like stacked and trench capacitor designs.

[0042] Further advantages of the preferred processes will be apparent from the discussion below.

[0043] Methods of Forming Conformal Capacitor Dielectrics

[0044] FIG. 4A generally illustrates a method of forming capacitor dielectric layers with high step coverage. The preferred method is a form of atomic layer deposition (ALD), whereby reactants are supplied to the workpiece in alternating pulses in a cycle. Preferably, each cycle forms no more than about one monolayer of material by adsorption and more preferably by chemisorption. The substrate temperature is kept within a window facilitating chemisorption. In particular, the substrate temperature is maintained at a temperature low enough to maintain intact bonds between adsorbed complex and the underlying surface, and to prevent decomposition of the precursors. On the other hand, the substrate temperature is maintained at a high enough level to avoid condensation of reactants and to provide the activation energy for the desired surface reactions in each phase. Of course, the appropriate temperature window for any given ALD reaction will depend upon the surface termination and reactant species involved.

[0045] Each pulse or phase of each cycle is preferably self-limiting in effect. In the examples set forth below, each of the phases are self-terminating (i.e., an adsorbed and preferably chemisorbed monolayer is left with a surface non-reactive with the chemistry of that phase). An excess of reactant precursors is supplied in each phase to saturate the structure surfaces. Surface saturation ensures reactant occupation of all available reactive sites (subject to physical size restraints, as discussed in more detail below), while self-termination prevents excess film growth at locations subject to longer exposure to the reactants. Systematic utilization of saturation through chemisorption, i.e., self-terminating chemistries, ensure excellent step coverage.

[0046] Prior to forming the dielectric layer, an integrated circuit is first partially fabricated to the point of constructing a capacitor lower or bottom electrode. Typically, the bottom electrode serves as a storage electrode in the memory cell. For purposes of the present description, however, the bottom electrode represents the first-formed capacitor electrode or plate, regardless of whether it serves as the storage or reference plate in the completed integrated circuit.

[0047] As illustrated in FIG. 4 A, the process in accordance with preferred binary material embodiments begins with formation 100 of a bottom electrode structure in an integrated circuit. The basic bottom electrode structure can be planar, such as the floating gate in an EEPROM device. Preferably, however, the bottom electrode conforms to a three-dimensional folding structure having a greater surface area than the substrate footprint occupied by the memory cell. More preferably, the capacitor bottom electrode takes the form of a stacked capacitor, such as the stud configuration illustrated in FIG. 1A or the cylindrical configuration illustrated in FIG. 1B . The skilled artisan will readily appreciate that the methods disclosed herein are also applicable to other stacked capacitor designs, such as crowns, finned structures, combs, pins, etc. In another arrangement, the capacitor bottom electrode is formed by conductively doping and/or conductively lining the walls of a trench formed within a semiconductor substrate, as illustrated in FIG. 2 .

[0048] After formation of the bottom electrode macrostructure, in either a stacked or trench arrangement, the bottom electrode is then provided 101 with a textured or roughened microstructure superimposed upon the three dimensional folding shape, further enhancing the surface area of the bottom electrode, preferably in the form of a layer of HSG silicon.

[0049] In an exemplary fabrication, conducted in a batch system sold under the trade name A600 UHV™ by ASM, International, Inc, the HSG silicon is formed by amorphous silicon deposition, seeding and redistribution anneal. A three-dimensional folding structure is formed of or coated with amorphous silicon. While in some processes, the amorphous silicon deposition can be conducted in situ within the same reaction chamber as the subsequent steps, in the illustrated embodiment, the folding amorphous silicon structure is formed prior transferring wafers to the A600 UHV™ system.

[0050] Within the preferred reactor, the amorphous silicon surface is seeded. In the illustrated embodiment, the temperature is raised to a level within the range of about 550° C. to 575° C. (e.g., about 560° C.) while the reactor pressure is preferably reduced to on the order of about 10 −5 Torr. A seeding gas in the preferred embodiment is monosilane, provided with a silane partial pressure of about 4×10 −6 Torr. After seeding, the density of which can be varied according to design, continued thermal treatment at the desired temperature results in a redistribution of mobile amorphous silicon. Silicon atoms tend to agglomerate about the seed or nucleation sites formed by the silane. The entire process takes on the order of about 10 minutes and 120 minutes for the batch system, including temperature ramp, seeding and anneal. The skilled artisan will readily appreciate numerous other techniques for forming HSG silicon.

[0051] The HSG grains produced by the preferred process can range in size from about 50 Å to 750 Å, with more a typical range of about 300 Å to 500 Å. The process conditions affecting nucleation density and HSG silicon grain size are typically selected to leave grains largely separated from one another. Such an arrangement maximizes electrode surface area within the constraint of allowing most of the subsequent dielectric and top electrode layers to fit between the grains. As will be appreciated from the enlarged views of FIGS. 7 through 10 , however, the grains randomly converge at some locations due to the inherently random seeding process. Moreover, the preferred dielectric and top electrode layers enable use of denser, less separated grains, thus increasing the usable surface area.

[0052] As will be appreciated by the skilled artisan, the bottom electrode preferably serves as the storage node of a memory cell in a dynamic random access memory (DRAM) array. After fabrication, the bottom electrode is typically isolated from the bottom electrodes of other cells across the array, as shown in FIGS. 1A, 1B and 2 .

[0053] The bottom electrode structure so formed is thereafter coated with high step coverage. In accordance with the preferred embodiments, the dielectric layer is formed by a periodic process in which each cycle forms no more than about one monolayer of dielectric material upon the workpiece in a self-limiting manner. Preferably, each cycle comprises at least two distinct phases, wherein each phase is a saturative reaction, i.e., self-limitingly, leaving no more than about one atomic monolayer of the desired dielectric material.

[0054] If necessary, the exposed surfaces of the bottom electrode (e.g., the HSG silicon of the preferred embodiments) are terminated 102 to react with the first phase of the ALD process. The first phases of the preferred metal oxide embodiments (see Tables I to V) are reactive, for example, with hydroxyl (OH) or ammonia (NH 3 ) termination. In the examples discussed below, silicon surfaces of HSG silicon will not generally require a separate termination. Exposure to a clean room environment results in native oxide formation that naturally provides OH termination 102 . Where HSG is formed in situ or in a cluster tool prior to dielectric formation, it may be desirable to expose the HSG to H 2 O vapor, for example, as a surface preparation or termination 102 treatment. In other arrangements (see the discussion of Tables II and III below and FIG. 8 ), metal oxides can also be formed directly on silicon nitride without a separate termination step. In other words, nitridation of HSG silicon can serve as the termination 102 .

[0055] After initial surface termination 102 , if necessary, a first chemistry is then supplied 104 to the workpiece. In accordance with the preferred metal oxide embodiments, discussed in more detail below with respect to FIG. 5 , the first chemistry comprises a metal-containing compound that is reactive with the terminated surfaces left by the previous step 102 . Accordingly, a metal complex replaces the surface termination by means of ligand exchange. The resultant metal-containing monolayer is desirably self-terminating, such that any excess constituents of the first chemistry do not further react with the monolayer formed by this process. Preferably a halide or organic ligand terminates the metal-containing monolayer.

[0056] The metal-containing reactive species is preferably supplied in gaseous form, and is accordingly referred to hereinbelow as a metal source gas. The first chemistry is then removed 106 from the reaction chamber. In the illustrated embodiments, step 106 merely entails stopping the flow of the first chemistry while continuing to flow a carrier gas for a sufficient time to diffuse or purge excess reactants and reactant by-products out of the reaction chamber, preferably with greater than about two reaction chamber volumes of the purge gas, more preferably with greater than about three chamber volumes. In the illustrated embodiment, the removal 106 comprises continuing to flow purge gas for between about 0.1 seconds and 20 seconds after stopping the flow of the first chemistry. Inter-pulse purging is described in co-pending U.S. patent application having Ser. No. 09/392,371, filed Sep. 8, 1999 and entitled IMPROVED APPARATUS AND METHOD FOR GROWTH OF A THIN FILM, the disclosure of which is incorporated herein by reference. In other arrangements, the chamber may be completely evacuated between alternating chemistries. See, for example, PCT publication number WO 96/17107, published Jun. 6, 1996, entitled METHOD AND APPARATUS FOR GROWING THIN FILMS, the disclosure of which is incorporated herein by reference. Together, the adsorption 104 and removal 106 of excess reactant and by-products represent a first phase in an ALD cycle.

[0057] When the unreacted (or excess) reactants of the first chemistry have been removed 106 from the chamber, a second chemistry is supplied 108 to the workpiece. The second chemistry desirably reacts with the self-terminated monolayer formed in step 104 . In the illustrated metal oxide embodiments, described in more detail below with respect to FIG. 5 , this reaction comprises supplying an oxygen source gas to the workpiece. Oxygen or an oxygen-containing complex from the oxygen source gas preferably reacts with upon the previously adsorbed metal complex to leave a metal oxide monolayer in place of the metal complex monolayer.

[0058] In other arrangements, the second chemistry may simply remove the ligand termination of the adsorbed metal complex monolayer formed in step 104 (e.g., by sublimation or reduction) or otherwise prepare the monolayer for oxidation or chemisorption of a further chemistry.

[0059] Desirably, the reaction 108 is also self-limiting. Reactants saturate the limited number of reaction sites left by step 104 . Temperature and pressure conditions are preferably arranged to avoid diffusion of reactants from the second chemistry through the monolayer to underlying materials. The second chemistry also leaves a surface termination that is not reactive with excess reactants in the second chemistry, thus operating to limit the deposition in a saturative reaction phase. In the illustrated embodiments of Tables I to V below, hydroxyl (OH) tails and oxygen bridge termination on a metal oxide monolayer are non-reactive with excess oxygen source gases of the second chemistry.

[0060] After a time period sufficient to completely saturate the surface of the metal-complex monolayer through chemisorption (or self-limiting reaction) of the second chemistry, the excess second chemistry is removed 110 from the workpiece. As with the removal 106 of the first chemistry, this step 110 preferably comprises stopping the flow of the second chemistry and continuing to flow carrier gas for a time period sufficient to purge excess reactants and reaction by-products of the second chemistry from the reaction chamber. For example, reactants and reaction by-products can be removed by flowing purge gas after stopping the flow of the first chemistry, preferably with at least about two chamber volumes of purge gas and more preferably with at least about three chamber volumes. In the illustrated embodiment, the removal 110 comprises continuing to flow purge gas for between about 0.1 seconds and 20 seconds after stopping the flow of the first chemistry. Together, the reaction 108 and removal 110 represent a second phase 111 in an ALD cycle.

[0061] In the illustrated embodiment, where two phases are alternated once the excess reactants and by-products of the second chemistry have been purged from the reaction chamber, the first phase of the ALD process is repeated. Accordingly, supplying 104 the first chemistry again to the workpiece forms another self-terminating monolayer.

[0062] The two phases 107 , 111 thus represent a cycle 115 repeated to form monolayers in an ALD process. The first chemistry generally reacts (in a ligand-exchange) with or chemisorbs upon the termination left by the second chemistry in the previous cycle. If necessary, the cycle 115 can be extended to include a distinct surface preparation, similar to step 102 , as shown in dotted lines in FIG. 4 . The cycle 115 then continues through steps 104 to 110 . This cycle 115 is repeated a sufficient number of times to produce a dielectric layer over the HSG silicon of a thickness sufficient to avoid current leakage during circuit operation. Alternatively, a thinner layer can be followed by further dielectric layers, deposited by a similar ALD process, to form a stack of dielectric sublayers, as will be better understood from the discussion of FIG. 9 below.

[0063] With reference to FIG. 4 B, additional chemistries can also be included in each cycle. In FIG. 4 B, steps corresponding to those of FIG. 4A are referenced by numerals with the same last two digits in a 200 series, rather than the 100 series of FIG. 4A . Accordingly, steps 200 - 210 are similar to corresponding steps 100 - 110 of FIG. 4A .

[0064] The illustrated cycle 215 of FIG. 4 B, however, extends to include two additional phases. The first phase 207 and second phase 211 form a self-terminated metal oxide or silicon oxide monolayer. A third phase 219 and fourth phase 223 form another self-terminated metal oxide or silicon oxide monolayer. Note that the composition of the second monolayer preferably differs from the composition of the first monolayer at the discretion of the recipe designer. See, e.g. the metal silicate example of Table VI below.

[0065] In particular, after a first metal/silicon phase 207 and first oxygen phase 211 form a first metal oxide or silicon oxide monolayer, a second metal or silicon source gas is supplied 216 to form a self-limiting or self-terminating metal or silicon complex monolayer over the previously formed metal/silicon oxide. Similar to the first metal/silicon phase 207 , the metal/silicon gas source can react by ligand-exchange (chemisorption) upon the previously formed metal/silicon oxide. Following another removal 218 (by evacuation or preferably by purging) of the reactants, a second oxygen gas source is supplied 220 and then removed 222 . The second oxygen step 220 (or oxygen phase 223 ) is also self-limiting. As with the first oxygen step 208 , the oxygen gas source can react by ligand-exchange (chemisorption).

[0066] Though the illustrated process includes four phases in each cycle 215 , the cycle 215 will be referred to herein as a “ternary cycle 215 ,” since it produces a ternary dielectric. This is due to the fact that the second phase 211 and fourth phase 223 both contribute the same element (oxygen) to the growing dielectric layer. Note that, in other arrangement, depending upon the desired oxygen content in the dielectric layer, either the second phase or the fourth phase can be omitted. In such a case, consecutive chemistries would be selected to effect ligand-exchange reactions to produce surface termination with small enough ligands to permit some diffusion of a subsequent chemistry, and/or to have intermediate reduction phases in place of the omitted oxygen phase.

[0067] The second metal/silicon source gas in the third phase 219 can be a metal halide or metallorganic precursor, producing a metal complex monolayer self-terminated with halide or organic ligands that are non-reactive with the second metal/silicon source gas. In the example of Table VI, however, the second metal/silicon source gas comprises a silicon source gas conducive to self-limiting chemisorption, such as 3-aminopropyltriethoxysilane (NH 2 CH 2 CH 2 CH 2 —Si(O—CH 2 CH 3 ) 3 or AMTES) or 3-aminopropyltrimethoxsilane (NH 2 CH 2 CH 2 CH 2 —Si(O—CH 3 ) 3 or AMTMS) compound, or a halosilane. Note that the sequence of the metal source and silicon source phases can be reversed.

[0068] The oxygen source gas of the fourth phase 220 can be the same or differ from that of the second phase 211 . The inventors have found certain oxidants (e.g., ozone) to be advantageous for oxidizing metal or silicon complex monolayers having organic ligands, whereas other oxidants (e.g., water) are more advantageous for halide-terminated metal or silicon complex monolayers. Accordingly, in the example of Table VI below, the oxidant of the fourth phase 223 differs from the oxidant of the third phase 219 , at least for those cycles in which the metal/silicon source of the third phase 219 differs from the metal/silicon source of the first phase 207 .

[0069] For a roughly one-to-one ratio of the different metals or metal:silicon in the resultant dielectric, the cycle 215 is repeated, as shown. In the example of Table VI below, for example, repeated cycles with metal, oxygen, silicon and oxygen phases, in sequence, produces a metal silicate layer. Alternatively, the illustrated cycle 215 for a ternary dielectric can be conducted after a string of binary cycles 115 ( FIG. 4A ), depending upon the desired ratio of the different metals in the resultant ternary dielectric. Conversely, a binary cycle 115 ( FIG. 4A ) can be conducted after a string of ternary cycles 215 . Software controlling the gas flow valves can be programmed, for example, to conduct a one ternary cycle 215 after every three binary cycles 115 ( FIG. 4A ). Such a process would produce roughly a 3:1 ratio of a first metal to a second metal (or silicon) in the dielectric layer. The skilled artisan will appreciate, in view of the disclosure herein, that the actual ratio would depend both upon the frequency with which the second metal is substituted in the process and upon the relative physical size of the chemisorbed molecules.

[0070] Though both the binary and ternary processes are illustrated in FIGS. 4A and 4B with an initial metal/silicon phase and a subsequent oxygen phase in the examples below, it will be understood that the cycles can begin with an oxygen phase, depending upon the lower surfaces and phase chemistries.

[0071] Methods of Forming Metal Oxide Dielectrics

[0072] FIG. 5 and Tables I to V below illustrate exemplary processes for forming metal oxide dielectrics over the HSG silicon of the bottom electrode. Table I exemplifies forming an oxide of a non-transition metal (e g., aluminum); Tables II and III exemplify forming an oxide of a Group V transition metal (e.g., vanadium, niobium, tantalum); and Tables IV and V exemplify forming an oxide of Group IV transition metals (e.g., titanium, zirconium, hafnium). For simplicity, like reference numerals are employed to refer to the phases and steps of the metal oxide examples ( FIG. 5 ) that correspond to the general description of FIG. 4A .

[0073] With reference now to FIG. 5, a gas flow sequence is represented in accordance with a particular embodiment. In the illustrated example, a high k dielectric, and more particularly a high k metal oxide, is formed by supplying the workpiece with a metal source gas alternately with an oxygen source gas. The first or metal phase 107 of each cycle chemisorbs a layer of metal-containing material, desirably in the absence of the oxygen source gas. The second or oxygen phase 111 of each cycle reacts or adsorbs an oxygen-containing material on the deposited metal-containing layer, desirably in the absence of the metal source gas. It will be understood that, in other arrangements, the order of the phases can be reversed, and that the reactant removal or purge steps can be considered part of the preceding or subsequent reactant pulse.

[0074] Surfaces upon which the dielectric material is to be formed are initially terminated to provide a surface that is reactive with the metal source gas. In the preferred embodiments, the exposed surfaces upon which deposition is desired include HSG silicon with OH terminating tails (see FIG. 7 ) and silicon nitride (see FIG. 8 ).

[0075] Most preferably, the metal phase 107 is self-limiting, such that no more than about one atomic monolayer is deposited during the first phase. Desirably, a volatile metal source gas is provided in a pulse 104 . Exemplary metal source gases include: trimethyl aluminum (TMA or (CH 3 ) 3 Al); aluminum chloride (AlCl 3 ); aluminum betadiketonates (e.g., Al(acac) 3 ); tantalum ethoxide (Ta(OCH 2 CH 3 ) 5 ); tantalum pentachloride (TaCl 5 ); pentakis(dimethylamino) tantalum (Ta[N(CH 3 )] 5 ); zirconium tetrachloride (ZrCl 4 ); zirconium butoxide (ZrOCH 2 CH 2 CH 3 ) 4 ); titanium tetrachloride (TiCl 4 ); titanium isopropoxide (Ti[OCH(CH 3 ) 3 ] 4 ); tetrakis(dimethylamino) titanium (Ti[N(CH 3 ) 2 ] 4 ); tetrakis (dimethylamino) titanium (Ti[N(CH 5 ) 2 ] 4 tungsten hexafluoride (WF 6 ); 3-aminopropyltriethoxysilane (NH 2 CH 2 CH 2 CH 2 —Si(O—CH 2 CH 3 ) 3 or AMTES); 3-aminopropyltrimethoxsilane (NH 2 CH 2 CH 2 CH 2 —Si(O—CH 3 ), or AMTMS); dichlorosilane (DCS); trichlorosilane (TCS); vanadium trichloride (VCl 3 ); vanadium acetylacetonate (V(acac) 3 ); niobium pentachloride (NbCl 5 ); niobium ethoxide (Nb(OCH 2 CH 3 ) 5 ); hafnilum tetrachloride (HfCl 4 ), etc.

[0076] After a sufficient time for the metal source gas to saturate surfaces of the bottom electrode, shutting off the flow of the metal source gas ends the metal pulse 104 . Preferably, carrier gas continues to flow in a purge 106 until the metal source gas is purged from the chamber.

[0077] During the pulse 104 , the metal source gas reacts with exposed surfaces of the workpiece to deposit or chemisorb a “monolayer” of metal complex. While theoretically the reactants will chemisorb at each available site on the exposed layer of the workpiece, physical size of the adsorbed complex (particularly with large terminating ligands) will generally limit coverage with each cycle to a fraction of a monolayer. In the example of Table I, the ALD process grows metal oxide layers at roughly 1 Å/cycle, such that a full monolayer effectively forms from material deposited approximately every 3 cycles for Al 2 O 3 , which has a bulk lattice parameter of about 3 Å. Each cycle is represented by a pair of metal source gas and oxygen source gas pulses. “Monolayer,” as used herein, therefore represents a fraction of a monolayer during deposition, referring primarily to the self-limiting effect of the pulse 104 .

[0078] In particular, the metal-containing species provided to the workpiece is self-terminating such that the adsorbed complex surface will not further react with the metal source gas. In the examples set forth below, TMA (Table I) leaves a monolayer of methyl-terminated aluminum. Tantalum ethoxide (Table II) leaves a monolayer of ethoxide tantalum. Similarly, other volatile metal halides will leave halide-terminated surfaces, and metallorganic precursors will leave surface terminated with organic ligands. Such surfaces do not further react with the metal source or other constituents of the reactant flow during the metal source gas pulse 104 . Because excess exposure to the reactants does not result in excess deposition, the chemistry during the metal phase 107 of the process is said to be saturative or self-limiting. Despite longer exposure to a greater concentration of reactants, deposition on upper surfaces of HSG silicon grains does not exceed deposition in neck regions between grains

[0079] In a second phase 111 of the cycle 115 , a pulse 108 of an oxygen source gas is then provided to the workpiece. In the illustrated examples, the oxygen source gas comprises water vapor (H 2 O) or ozone. Other suitable oxidants include: hydrogen peroxide (H 2 O 2 ); methanol (CH 3 OH); ethanol (CH 3 CH 2 OH), nitrous oxide (N 2 O, NO 2 ); O radicals; etc. Radicals can be provided by remote plasma sources connected to the reaction chamber, and an ozone generator can similarly provide ozone (O3). Preferably, the second phase 111 is maintained for sufficient time to fully expose the monolayer of metal complex left by the first phase 107 to the oxygen source gas. After a sufficient time for the oxygen source gas to saturate the metal-containing monolayer over the HSG silicon layer, shutting off the flow of the oxygen source gas ends the oxygen pulse 108 . Preferably, carrier gas continues to flow in a purge step 110 until the oxygen source gas is purged from the chamber.

[0080] During the oxygen pulse 108 , the oxygen source gas reacts with or chemisorbs upon the self-terminated metal complex monolayer left by the first phase 107 . In the illustrated embodiments, this chemisorption comprises a saturative ligand-exchange reaction, replacing the organic ligand or halide termination of the metal-containing monolayer with oxygen or an oxygen complex. Metal oxide is thereby formed, preferably in a single monolayer. Desirably, the process leaves a stoichiometric metal oxide, with hydroxyl and oxygen bridge termination. As discussed with respect to the metal phase 107 , the monolayer need not occupy all available sites, due the physical size of the adsorbed complex. However, the second phase 111 also has a self-limiting effect.

[0081] In particular, the oxygen source gas reacts with the ligand of the metal complex chemisorbed onto the workpiece surface during the previous pulse of metal source gas. The reaction is also surface limiting or terminating, since the oxidant during the pulse 108 will not react with the hydroxyl and oxygen bridge termination of the metal oxide monolayer. Moreover, temperature and pressure conditions are arranged to avoid diffusion of the oxidant through the metal monolayer to underlying materials. Despite longer exposure to a greater concentration of reactants in this saturative, self-limiting reaction phase 111 , the thickness of the metal oxide formed on upper surfaces of the HSG silicon grains does not exceed the thickness of the metal oxide formed in the neck regions between grains.

[0082] The metal phase 107 (including metal source pulse 104 and purge 106 ) and oxygen phase 108 (including oxygen source pulse 108 and purge 110 ) together define a cycle 15 that is repeated in an ALD process. After the initial cycle 115 , a second cycle 115 a is conducted, wherein a metal source gas pulse 104 a is again supplied. The metal source gas chemisorbs a metal complex on the surface of the metal oxide formed in the previous cycle 115 . The metal-containing species readily react with the exposed surface, depositing another monolayer or fraction of a monolayer of metal complex and again leaving a self-terminated surface that does not further react with the metal source gas. Metal source gas flow 104 a is stopped and purged 106 a from the chamber, and a second phase 111 a of the second cycle 115 a provides oxygen source gas to oxidize the second metal monolayer.

[0083] The cycle 115 a is repeated at least about 10 times, and more preferably at least about 20 times, until a sufficiently thick metal oxide is formed to avoid leakage during memory cell operation. Advantageously, layers having a uniform thickness between about 10 Å and 200 Å, and more preferably between about 25 Å and 100 Å, can be formed with near perfect step coverage by the methods of the preferred embodiments.

[0084] The tables below provide exemplary process recipes for forming metal oxide and ternary dielectric layers suitable for capacitor dielectric applications in DRAM memory cells for ultra large scale integrated processing. The dielectrics are particularly suited to deposition over HSG silicon. Each of the process recipes represents one cycle in a single-wafer process module. In particular, the illustrated parameters were developed for use in the single-wafer ALD module commercially available under the trade name Pulsar 2000™, available commercially from ASM Microchemistry Ltd. of Finland.

[0085] Note that the parameters in the tables below are exemplary only. Each process phase is desirably arranged to saturate the bottom electrode surfaces. Purge steps are arranged to remove reactants between reactive phases from the reaction chamber. The illustrative ALD processes achieve better than about 95% thickness uniformity, and more preferably greater than about 98% thickness uniformity over HSG grains with average gain sizes of about 400 Å. Thickness uniformity, as used herein, is defined as the percentage of a thickness minimum as a percentage of the thickness maximum. In view of the disclosure herein, the skilled artisan can readily modify, substitute or otherwise alter deposition conditions for different reaction chambers and for different selected conditions to achieve saturated, self-terminating phases at acceptable deposition rates.

[0086] Advantageously, the ALD processes described herein are relatively insensitive to pressure and reactant concentration, as long as the reactant supply is sufficient to saturate the textured surfaces. Furthermore, the processes can operate at low temperatures. Workpiece temperature is preferably maintained throughout the process between about 150° C. and 350° C. to achieve relatively fast deposition rates while conserving thermal budgets. More preferably, the temperature is maintained between about 220° C. and 300° C., depending upon the reactants. Pressure in the chamber can range from the milliTorr range to super-atmospheric, but is preferably maintained between about 1 Torr and 500 Torr, more preferably between about 1 Torr and 10 Torr. 1

[0087] Table I above presents parameters for ALD of an aluminum oxide (Al 2 O 3 ) dielectric over HSG silicon. The exemplary metal source gas comprises trimethyl aluminum (TMA), the carrier gas comprises nitrogen (N 2 ) and the oxygen source gas preferably comprises water vapor (H 2 O). The temperature during the process is preferably kept between about 150° C. and 350° C., and more preferably at about 300° C.

[0088] In the first phase of the first cycle, TMA chemisorbs upon the HSG silicon surfaces of the bottom electrode. The metal source gas preferably comprises a sufficient percentage of the carrier flow, given the other process parameters, to saturate the bottom electrode surfaces. A monolayer of aluminum complex is left upon the HSG silicon surfaces, and this monolayer is self-terminated with methyl tails.

[0089] After the TMA flow is stopped and purged by continued flow of carrier gas, a pulse of H 2 O is supplied to the workpiece. The water readily reacts with the methyl-terminated surface of the metal monolayer in a ligand-exchange reaction, forming a monolayer of aluminum oxide (Al 2 O 3 ). The reaction is limited by the number of available metal complexes previously chemisorbed. The reaction is furthermore self-limiting in that neither water nor the carrier gas further reacts with the hydroxyl and oxygen bridge termination of the resulting aluminum oxide monolayer. The preferred temperature and pressure parameters, moreover, inhibit diffusion of water or reaction by-products through the metal monolayer.

[0090] In the next cycle, the first phase introduces TMA, which readily reacts with the surface of the aluminum oxide monolayer, again leaving a methyl-terminated aluminum layer above the first metal oxide layer. The second phase of the second cycle is then as described with respect to the first cycle. These cycles are repeated until the desired thickness of aluminum oxide is formed.

[0091] In the illustrated embodiment, carrier gas continues to flow at a constant rate during both phases of each cycle. It will be understood, however, that reactants can be removed by evacuation of the chamber between alternating gas pulses. In one arrangement, the preferred reactor incorporates hardware and software to maintain a constant pressure during the pulsed deposition. The disclosures of U.S. Pat. No. 4,747,367, issued May 31, 1988 to Posa and U.S Pat. No. 4,761,269, issued Aug. 2, 1988 to Conger et al., are incorporated herein by reference.

[0092] Radicals provided by plasma generators can facilitate deposition of metal-containing layers at the low temperatures of ALD processing. Structures and methods of depositing layers with radical enhancement are provided in patent application having Ser. No. 09/392,371, filed Sep. 8, 1999 and entitled IMPROVED APPARATUS AND METHOD FOR GROWTH OF A THIN FILM, the disclosure of which is incorporated by reference hereinabove. Another exemplary ALD process flow is provided in U.S. Pat. No. 5,916,365 to Shermnan, issued Jun. 29, 1999, the disclosure of which is incorporated herein by reference. 2

[0093] Table II above presents parameters for ALD of a tantalum oxide (Ta 2 O 5 ) over HSG silicon of a capacitor bottom electrode. Preferably, the illustrated dielectric deposition is preceded by formation of a barrier layer to protect the HSG silicon from oxidation. In the illustrated embodiment, a dielectric barrier is formed, specifically comprising silicon nitride (Si 3 N 4 ). Advantageously, silicon nitride can be formed over HSG silicon with near perfect conformality by thermally nitriding the silicon surfaces. In other arrangements, a thin oxide layer can be first grown (e.g., by thermal oxidation) over the HSG silicon, followed by thermal nitridation of the oxide surface, as is known in the art.

[0094] Following formation of the barrier layer, Ta 2 O 5 is formed in an ALD process. As indicated in Table II, the illustrated metal source gas comprises tantalum ethoxide (Ta(OCH 2 CH 3 ) 5 ); the carrier gas comprises nitrogen (N 2 ); and the oxygen source gas preferably comprises ozone (O 3 ). The temperature during the process is preferably kept between about 150° C. and 300° C., and more preferably at about 220° C.

[0095] In the first phase of the first cycle, tantalum ethoxide chemisorbs upon the nitridized surfaces of the HSG silicon. The metal source gas preferably comprises a sufficient percentage of the carrier flow, given the other process parameters, to saturate the nitride-coated HSG silicon surfaces. A monolayer of tantalum complex is left upon the textured surfaces, and this monolayer is self-terminated with ethoxide tails.

[0096] After the metal source gas flow is stopped and purged by continued flow of carrier gas, a pulse of ozone is supplied to the workpiece. Ozone preferably comprises a sufficient percentage of the carrier flow, given the other process parameters, to saturate the surface of the metal-containing monolayer. The ozone readily reacts with the ethoxide-terminated surface of the metal-containing monolayer in a ligand-exchange reaction, forming a monolayer of tantalum oxide (Ta 2 O 5 ). The reaction is limited by the number of available metal complexes previously chemisorbed. Neither ozone nor the carrier gas further reacts with the resulting tantalum oxide monolayer. Ozone causes the organic ligand to burn, liberating CO 2 and H 2 O, and the monolayer is left with hydroxyl and oxygen bridge termination. The preferred temperature and pressure parameters, moreover, inhibit diffusion of ozone and reaction by-products through the metal monolayer.

[0097] In the next cycle, the first phase introduces tantalum ethoxide, which readily reacts with the surface of the tantalum oxide monolayer, again leaving an ethoxide-terminated tantalum layer. The second phase of the second cycle is then as described with respect to the first cycle. These cycles are repeated until the desired thickness of tantalum oxide is formed. Preferably, between about 80 and 200 cycles are conducted to grow between about 40 Å and 100 Å of Ta 2 O 3 . More preferably, between about 80 and 100 cycles are conducted to grow between about 40 Å and 50 Å

[0098] In the illustrated embodiment, carrier gas continues to flow at a constant rate during both phases of each cycle. It will be understood, however, that reactants can be removed by evacuation of the chamber between alternating gas pulses. In one arrangement, the preferred reactor incorporates hardware and software to maintain a constant pressure during the pulsed deposition. The disclosures of U.S. Pat. No. 4,747,367, issued May 31, 1988 to Posa and U.S. Pat. No. 4,761,269, issued Aug. 2, 1988 to Conger et al., are incorporated herein by reference.

[0099] An amorphous Ta 2 O, dielectric layer is left with only trace amounts of carbon. This layer can be annealed for a crystallized dielectric, if desired. The dielectric constant of the layer is between about 20 and 25. 3

[0100] Table III above presents parameters for another ALD process for depositing tantalum oxide (Ta 2 O 5 ) over HSG silicon of a capacitor bottom electrode. Following formation of the silicon nitride barrier layer, as described above, Ta 2 O 5 is formed in an ALD process. As indicated in Table III, the preferred metal source gas comprises tantalum chloride (TaCl 5 ); the carrier gas again comprises nitrogen (N 2 ); and the oxygen source gas preferably comprises water vapor (H 2 O). Temperatures during the process are preferably between about 150° C. and 300° C., and more preferably about 300° C.

[0101] In the first phase of the first cycle, tantalum chloride chemisorbs upon the silicon nitridized surfaces of the HSG. The metal source gas preferably comprises a sufficient percentage of the carrier flow, given the other process parameters, to saturate the nitride-coated HSG silicon surfaces. A monolayer of tantalum complex is left upon the textured surfaces, and this monolayer is self-terminated with chloride tails.

[0102] After the TaCl 5 flow is stopped and purged by continued flow of carrier gas, a pulse of water vapor is supplied to the workpiece. Water vapor preferably comprises a sufficient percentage of the carrier flow, given the other process parameters, to saturate the surface of the metal-containing monolayer. The water readily reacts with the chloride-terminated surface of the metal-containing monolayer in a ligand-exchange reaction, forming a monolayer of tantalum oxide (Ta 2 O). The reaction is limited by the number of available metal chloride complexes previously chemisorbed. Neither water nor the carrier gas further reacts with the hydroxyl and oxygen bridge termination of the resulting tantalum oxide monolayer. The preferred temperature and pressure parameters, moreover, inhibit diffusion of water and reaction by-products through the metal monolayer.

[0103] In the next cycle, the first phase introduces TaCl 5 , which readily reacts with the surface of the tantalum oxide monolayer, again leaving a chloride-terminated tantalum layer. The second phase of the second cycle is then as described with respect to the first cycle. These cycles are repeated until the desired thickness of tantalum oxide is formed, as described with respect to the preceding example.

[0104] As mentioned above, the chamber can be evacuated to remove reactants between pulses, rather than purged by a steady carrier gas flow as shown, though inter-pulse purging is preferred.

[0105] An amorphous Ta 2 O 5 dielectric layer is left with only trace amounts of chlorine. This layer can be annealed for a crystallized dielectric, if desired. The dielectric constant of the layer is between about 20 and 25. 4

[0106] Table IV above presents parameters for ALD of zirconium oxide (ZrO 2 ). As noted, the metal source comprises zirconium chloride (ZrCl 4 ); the carrier gas comprises nitrogen (N 2 ); and the oxygen source gas preferably comprises water vapor (H 2 O). During each of the reaction phases, the reactants are supplied in sufficient quantity for the given other parameters to saturate the surface. Temperatures during the process preferably fall between about 200° C. and 500° C. For an amorphous ZrO 2 layer, the temperature is more preferably at the low end of this range, between about 200° C. and 250° C., and most preferably at about 225° C. For a crystalline film, the temperature is more preferably at the high end of this range, between about 250° C. and 500° C., and most preferably about 300° C. As will be appreciated by the skilled artisan, however, mixtures of amorphous and crystalline composition result at the boundary of these two regimes. The illustrated process produces a largely crystalline ZrO 2 film.

[0107] In this case, the metal monolayer formed in the metal phase is self-terminated with chloride, which does not readily react with excess ZrCl 4 under the preferred conditions. The preferred oxygen source gas. However, reacts with or adsorbs upon the chloride-terminated surface during the oxygen phase in a ligand-exchange reaction limited by the supply of zirconium chloride complexes previously adsorbed. Moreover, oxidation leaves a hydroxyl and oxygen bridge termination that does not further react with excess oxidant in the saturative phase.

[0108] Preferably, between about 30 and 80 cycles are conducted to grow between about 20 Å and 60 Å of ZrO 2 . More preferably, between about 30 and 50 cycles are conducted to grow between about 20 Å and 40 Å. The dielectric constant of the layer is between about 18 and 24. 5

[0109] Table V above presents parameters for ALD of titanium oxide (TiO 2 ). As noted, the metal source comprises titanium tetrachloride (TiCl 4 ); the carrier gas comprises nitrogen (N 2 ); and the oxygen source gas preferably comprises water vapor (H 2 O). During each of the reaction phases, the reactants are supplied in sufficient quantity for the given other parameters to saturate the surface.

[0110] As described with respect to ZrO 2 in the preceding example, temperatures is preferably kept at a level between about 200° C. and 500° C. In the illustrated embodiment, however, the illustrated embodiment employs a temperature between about 250° C. and 500° C., and most preferably about 300° C.

[0111] In this case, the metal monolayer formed in the metal phase is self-terminated with chloride, which does not readily react with TiCl 4 under the preferred conditions. The preferred oxygen source gas, however, reacts with or adsorbs upon the chloride-terminated surface during the oxygen phase in a reaction limited by the supply of titanium chloride complexes previously adsorbed. Moreover, oxidation leaves a hydroxyl and oxygen bridge and termination that does not further react with excess oxidant in the saturative phase.

[0112] Preferably, between about 30 and 80 cycles are conducted to grow between about 20 Å and 60 Å of TiO 2 . More preferably, between about 30 and 50 cycles are conducted to grow between about 20 Å and 40 Å. The dielectric constant of the layer is between about 15 and 25.

[0113] Method of Forming Ternary Dielectric Layers

[0114] As discussed with respect to FIG. 4 B, the principles of ALD described above with respect to metal oxide capacitor dielectrics, can also be extended to depositing ternary materials and more complex materials.

[0115] With reference to FIG. 6, a gas flow schematic is shown for a general process of forming ternary structures, specifically for forming mixed or compound metal oxides or metal silicates. Though the example of Table VI below relates to a metal silicate layer, formed by metal/oxygen1/silicon/oxygen2 phases, in that order, the skilled artisan will readily appreciate that the disclosed sequence can be altered for silicate materials (e.g., silicon/oxygen/metal/oxygen) or adapted for complex metal oxides (e.g., first metal/oxygen/second metal/ oxygen). Furthermore, the illustrated sequence can be extended to encompass more complex materials incorporating multiple elements. For convenience, the reference numerals of FIG. 4B are utilized to refer to like process steps, phases and sequences.

[0116] As illustrated, the process comprises four phases to each cycle, wherein each phase comprises a reactant phase and a purge phase. A first metal or silicon phase 207 is followed by a first oxygen phase 211 , a second metal or silicon phase 219 , and a second oxygen phase 223 , in sequence. The cycle is then repeated. As previously noted, in other arrangements, the first or fourth phase can be omitted every cycle or every few cycles, if a low oxygen content is desired. In such a case, chemistries should be selected to permit reaction between deposited monolayers and subsequent chemistries. As will be better understood from the discussion of Table VI below, the first oxygen source (in the second phase 211 ) can be, but is not necessarily, the same as the second oxygen source (in the fourth phase 223 ). After four phases 207 , 211 , 219 , 223 complete the first cycle 215 , a second, similar cycle 215 a can be conducted to continue ternary growth. These cycles 215, 215 a continues until the ternary material of interest is thick enough to avoid current leakage but thin enough to exhibit high capacitance.