Selective thin film etch process

Abstract: A plasma process using a reactant gas mixture of fluorinated etching gas and oxygen for selectively etching a thin film of material such as silicon nitride with high selectivity for a silicon oxide underlayer and, preferably, for a photoresist overlayer mask.

Description: The present invention relates to the selective, preferably anisotropic, etching of silicon nitride films, formed over silicon dioxide. In particular, our invention relates to a process for etching silicon nitride anisotropically with a high selectivity to the underlying silicon dioxide and with a controlled silicon nitride profile and controlled silicon dioxide loss or gain. The composite silicon nitride-over-silicon oxide has a number of applications in integrated circuits. For example, nitride-over-oxide may be used as an oxidation mask to selectively expose field areas of IC (integrated circuit) wafers during LOCOS formation of the field isolation oxide. In such applications, the underlying oxide may be very thin. During the patterning of the silicon nitride LOCOS mask, it is necessary to precisely replicate the lithographic mask, such a photoresist, in the silicon nitride without dimensional loss, with good resolution and without etching of (i.e., with suitably high selectivity for) the overlying photoresist mask and the underlying thin oxide. When the nitride is removed subsequently from the active areas, selectivity for photoresist is not a concern, because the photoresist is stripped prior to the LOCOS oxidation. However, preventing degradation of removal of the thin oxide is still very much a concern. Fluorocarbon etchants such as CH 3 F and CH 2 F 2 and SF 6 and NF 3 have been used to etch silicon nitride. Fluorocarbon etchants may form non-volatile carbon-containing organic polymers which deposit on the oxide and, therefore, increase the etch selectivity. However, carbon forms particulates and thus, results in an undesirably dirty process, particularly for LSI (large scale integrated) and VLSI (very large scale integrated) circuits, which are susceptible to even a relatively few very small particulates. In addition, organic polymer layers may deposit, sometimes indiscriminately, within the reactor, necessitating relatively frequent cleaning of the reactor. FR-A-2408913 discloses a gas plasma process and gas mixture useful for the removal of materials in the manufacture of semi-conductor devices. Substrate wafers or semi-conductor devices are exposed to a gaseous plasma containing SiF 4 or SiF 4 and oxygen for a time to effect a desired removal of material from the wafer or device. The process/gas mixture are intended for selective etching of Si3N 4 and the stripping of photoresist, as well as the etching of materials such as silicon and compounds containing silicon. US-A-4568410 discloses etching of silicon nitride at a rapid rate selectively against oxide in a gas plasma formed from a gas mixture comprising 10-20 parts NF 3 to 20-35 part O 2 , by volume. Silicon nitride etch rates in the range 55 to 75 milli-microns per minute are obtained at nitride/oxide etch rate ratios of 8-11:1. It is a primary object of the present invention to selectively etch a thin film such as silicon nitride formed on a silicon dioxide underlayer. It is a related objective to provide a process which achieves selective anisotropic etching of silicon nitride-over-silicon dioxide with a resulting controlled anisotropic nitride etch profile and controlled selectivity (either gain or loss) for the underlying oxide. It is another related object to provide such a process which also achieves controlled selectivity for photoresist masks. These objects are solved by the process according to claim 1. In one aspect, our process is adapted to selectively (and anisotropically) etch a silicon nitride layer constituent of a body comprising a silicon nitride layer formed over a silicon oxide underlayer with controlled selectivity for the silicon oxide underlayer and comprises exposing the body to a plasma formed from a reactant gas flow of SiF 4 , oxygen and NF 3 . More specifically, the process for etching a silicon nitride layer constituent of a body comprising a layer of silicon nitride over a silicon oxide underlayer, with controlled high selectivity for the silicon oxide underlayer, using a photoresist etch mask formed over the silicon nitride, in a plasma etching chamber, comprises positioning the masked body of the etch chamber and communicating into the chamber a selected reactive gas mixture comprising NF 3, NiF 4 and O 2 for etching the silicon nitride with a high selectivity for the photoresist and for the oxide underlayer. The following is a description of a specific embodiment of the invention, reference being made to the accompanying drawings in which: FIG. 1 is a schematic illustration of a suitable plasma etching system for practicing the present process. FIGS. 2-5 depict trend lines showing the effect of the various gases on oxide and nitride etch rates. 1. Overall Process Our invention uses oxygen-containing fluorinated gas chemistry in a vacuum plasma reactor to etch silicon nitride with controlled anisotropy, accompanied by high selectivity to organic photoresist masks and controlled selectivity to oxide. This controlled silicon nitride etch is a simple, one-step process, which increases repeatability, decreases material costs and enhances operator control. In addition, the increased selectivity to the oxide underlayer increases process yields and makes it easier to adapt the process to other applications. The preferred reactive gas chemistry comprises O 2 /SiF 4 and, more particularly, NF 3 /O 2 /SiF 4 . SiF 4 is the selectivity and nitride etch agent (see Reaction A). NF 3 can be the main nitride etchant (see Reaction B). The O 2 combines with silicon from the SiF 4 to selectively form a silicon oxide-containing deposit on the oxide underlayer and, thus, increase the selectivity for oxide layers (see Reaction A). For example, typically, increasing the number of silicon nitride-containing wafers decreases the nitride etch rate, but increasing the NF 3 flow rate thus compensates for the increased number of wafers, by increasing the nitride etch rate, even where other parameters are maintained constant. The addition of NF 3 increases the usable range of the process, i.e., the process window. 2. Process Trends/Trend Lines The versatility and advantages of our present process is demonstrated by the ability to use the selected process gases to tailor the etch selectivity for photoresist etch masks and to control the rate of deposition of the silicon oxide-containing compounds and thereby control the loss (or gain) of oxide during the process by changing the flow rate and flow rate ratios of the three main gaseous reactants NF 3 , O 2 and SiF 4 . These results are achieved using a standard, unaltered reactor 10, FIG. 1. The effects of the selected process gases are summarized below. The applicable equilibrium reactions for the SiF 4 , NF 3 and O 2 are: Reaction A dominates the selectivity mechanism, because the SiO 2 is deposited and the fluorine is a nitride etchant. As shown in Reaction B, the fluorine increases the nitride etch rate. The nitride etch rate is directly proportional to the flow rate of the SiF 4 , which is used here as the main nitride etchant. As mentioned above and as depicted in FIGS. 2 and 3, increasing the flow rate of NF 3 increases both the nitride etch rate and the oxide loss. The oxide etch rate is affected by the photoresist coverage on the wafer. Specifically, the oxide etch rate is inversely proportional to the area of the wafer covered by the photoresist at fixed process conditions. Decreasing/increasing the photoresist coverage increases/decreases the oxide loss during etching. The photoresist acts as an oxygen getter which slows down or prohibits the formation of and the deposition of SiO x , which is the key factor in controlling oxide loss or gain and selectivity. However, as discussed below, an IC design and associated nitride etching step which require a large area photoresist coverage can be compensated for by increasing the oxygen flow rate. As mentioned previously, the oxide etch/deposition rate is affected and controllable by changing the percent of oxygen in the total gas flow. In fact, as shown in FIGS. 4 and 5, both the nitride etch rate and the oxide etch rate are inversely proportional to the oxygen proportion of the total flow. However, the responses of the oxide and nitride etch rates are different as the oxygen flow rate is increased and this is responsible for our ability to exploit the selectivity mechanism. Moreover, the addition of NF 3 contributes to the control of the selectivity mechanism. Referring further to FIG. 4, decreasing/increasing the flow rate of the oxygen relative to the other gases also decreases/increases the selected deposition of SiO x , typically SiO 2 , on the oxide and consequently increases/decreases the oxide loss during etching. See Reaction A. Increasing the flow rate of oxygen can increase the silicon oxide deposition rates sufficiently to provide infinite selectivity to oxide (zero etch rate) and, in fact, to provide net oxide deposition or gain rather than loss. In effect, varying the oxygen flow rate ratio permits the selection of oxide etch/deposition from a continuum of rates, that is, from high etch rates at one end of the spectrum, to zero etch/deposition, to deposition. Furthermore, our understanding of the different effects of photoresist coverage and oxide flow on the oxide etch/deposition rates has made it possible to obtain the low oxide etch rates and high selectivity to different photoresist coverage by adjusting the O 2 flow rate. That is, large area photoresist coverage can be compensated by increasing the oxygen flow. SiF 4 is an etchant (the nitride etch rate is proportional to the SiF 4 flow). In addition, the effect of SiF 4 flow on oxide etch/deposition is similar to that of oxygen flow in that the oxide (specifically SiO 2 ) etch rate is inversely proportional to the SiF 4 flow. Decreasing/increasing the flow rate of the SiF 4 increases/decreases the oxide loss. 3. Examples and Applications The tables listed below summarize optimum values and ranges of preferred and useful values of parameters for etching silicon nitride over silicon dioxide using the AME 8110 low pressure ion-assisted plasma reactor. This reactor is available from Applied Materials, Inc., Santa Clara, California. The AME 8110 and, more generally, the 8100 series of low pressure reactive ion etching (RIE) mode plasma etching reactors, are schematically illustrated as system 10 in FIG. 1. The RIE system 10 includes a cylindrical reaction chamber 11 and a hexagonal cathode 12 which illustratively holds twenty-four wafers, four to a facet, and is connected to an RF power supply 13. An exhaust port 14 communicates between the interior of the reaction chamber 11 and a vacuum pump. The walls of the reaction chamber 11 and the base plate 16 form the grounded anode of the system. A supply of reactive gas from gas supply 17 is communicated to the interior of the chamber 11 through an entrance port 18 and through a conduit arrangement 19 to a gas distribution ring 20 at the top of the chamber. The geometry of the reactor system 10 is asymmetric. That is, the anode-to-cathode ratio is slightly greater than 2-to-1, resulting in high energy bombardment of the cathode surface 12 relative to the anode surface 11. Such a design provides lower power density and bettern etch uniformity, decreases contamination from the chamber walls and facilitates achievement of etch anisotropy. In addition, the cathode structure configuration allows all twenty-four wafers to be vertically oriented during the process to minimize wafer exposure to particulates. In such RIE mode systems, a highly directional mechanical ion bombardment etch component dominates the more isotropic chemical component and imparts high anisotropy to the etching characteristics of the system. Consequently, RIE mode systems are preferred for the etching fabrication steps of highly dense, small feature size IC applications such as LSI and VLSI circuits. However, the use of the AME 8110 etcher and 8100 series etchers are to be considered illustrative only. The process also has been used successfully in the 8300 series etchers, which also are available from Applied Materials, Inc. of Santa Clara, California. More generally, the present process is primarily chemically driven and, thus, should apply to all plasma state etching systems capable of handling the prescribed gases. The three tables describe three increasingly specific useful ranges of process parameters for etching silicon nitride without damaging the oxide underlayer. That is, Table 1 describes a range of parameters which are expected to provide useful results based upon the data reflected in Tables 2 and 3. Moreover, because this process is chemically driven, it will have applicability to any plasma type system and, e.g., to a much broader range of pressures than are specified in the tables. Table 2 describes a narrower and, thus, more specific set of process parameter ranges which provide a more optimum combination of high silicon nitride etch rate, high selectivity for photoresist and high selectivity for oxide underlayers. Table 3 lists Etch Parameters Silicon Nitride/SiO 2 Process Parameters 1. Useful Range 2. Preferred Range 3. Optimum Value Total Gas Flow, sccm 10-400 50-100 78 NF 3 0-100 0-50 13 SiF 4 0-100 10-50 30 O 2 0-100 10-50 15 He 0-100 20-50 20 Chamber Pressure, mT (IT = 133.3 Pa) 10-150 20-50 30 Residence Time (sec.) 0.5-30 5-15 ∼9 Total Power Setting 8100 (w) 100-1500 100-700 600 Power Density (w/cm 2 ) 0.05-0.80 0.05-0.17 0.15 Etch Rate, Ang./min. 0-500 100-200 150 Selectivity for Photoresists (AZ 1470) ≥0:5 1:1 1:1 Selectivity for Underlayer: Composite >3:1 >5:1 15:1 Composite >5:1 >10:1 25:1 a specific narrow set of process parameters which are presently preferred in that they provide a combination of high nitride etch rates, adequate selectivity for photoresist and very high selectivity for oxide underlayers for a full load of twenty-four, six-inch wafers. In general, the tables are self-explanatory. As a group and as indicated, they involve etching a layer of thermal LPCVD silicon nitride or plasma nitride of approximate thickness (low pressure chemical vapor deposition) 1000 - 3000 Angstroms (10Å = 1 nm) formed over a thermally-grown silicon dioxide layer of thickness 80 -1000 Angstroms, using an 0.6 - 1.5 microns thick AZ1470 organic photoresist mask. Briefly, the exemplary etch process involves positioning one or more wafers containing the photoresist mask/nitride/oxide composite on the facets within the 8110 etch system, and after standard cleaning, seasoning and calibrating steps, applying gas at the stated flow rates for the given residence time and using the given chamber pressure and power setting. As indicated, the results are quite good. Selectivity for photoresist is ≥ 0:5, 1:1 and 1:1 for the broad, optimum and preferred full load ranges. The selectivity for the thermal oxide underlayer associated with the thermal LPCVD nitride is > 3:1, > 5:1 and about 15:1, respectively, for the three ranges. Also, the selectivity for the thermal oxide underlayer is > 5:1, > 10:1 and about 25:1, respectively, for the plasma nitride. Our process provides excellent linewidth control and a vertical nitride profile, minimizes linewidth loss, and minimizes bird's beak encrochment during LOCOS thermal oxidation, allowing better channel width definition for MOS devices. Overall uniformity is ± 4 percent as compared to ± 10 percent for prior practices using the 8110 with prior art high selectivity-to-oxide processes. In addition, because of the high selectivity and excellent uniformity, the uniformity of the remaining thermal oxide is much better than that provided by prior art processes. As indicated in Tables 2 and 3, the proper flow ratios of NF 3 , O 2 and SiF 4 are very important in achieving and controlling high selectivity for oxide. Also, the pressure range is very important to controlling and maintaining anisotropy and critical dimensions. It is expected that a substantial increase in pressure in the AME 8110 reactor would decrease critical dimension control and, possibly, etch rate uniformity. As indicated in the tables, an inert gas such as helium can be added to the NF 3 /SiF 4 /O 2 reactant gas composition, for the purpose of improving uniformity. Furthermore, inert gas such as helium or argon may be added in controlled amounts for the purpose of sputtering. Also, Freon-containing gases defined by the family C n H y F x X z could be added to increase the selectivity to the photoresist. In general, the above-described process can be adapted readily to etch films that form volatile products with fluorine chemistries, wherever high selectivity to underlying or masking silicon oxide is required. Thus, in addition to etching silicon nitride using NF 3 /SiF 4 /O 2 and NF 3 /SiF 4 /O 2 /He, the process is readily adaptable to selectively etch both doped and undoped polysilicon formed over silicon dioxide underlayers using NF 3 /SiF 4 /O 2 /C n H y F x X z reactive gases; to selectively etch tungsten over silicon dioxide underlayers using NF 3 /SiF 4 /O 2 /C n H y F x X z reactive gases; and to selectively etch single crystal silicon, both doped and undoped, with high selectivity to underlying silicon dioxide and/or a silicon dioxide mask using NF 3 /SiF 4 /O 2 . One such application is single crystal silicon trench etching. Also, it may be possible to extend the process to planar deposition of plasma silicon dioxides over polysilicon or aluminum lines using deposition and etch back. Planar deposition of silicon dioxide could be used for device passivation. The batch in-situ multi-step process capabilities of the AME 8100 and the AME 8300 reactive ion etch systems could be successfully applied to the present invention to manufacture one megabit and larger buried capacitor designs. Other applications include the isotropic removal of organic materials (such as photoresist and polyimides) for profile control using multi-step contouring approaches.

Claims: A process for selectively etching silicon nitride with high selectivity with respect to photoresist and silicon oxide using a gas mixture, characterised in that the gas mixture comprises SiF 4 , oxygen and NF 3 . A process for selectively etching silicon nitride as in claim 1, wherein the silicon nitride is a layer over a silicon oxide underlayer and has a photoresist mask formed thereon. A process as claimed in claim 1, characterised in that the reactant gas flow comprises a freon-containing gas for increasing the selectivity for photoresist. A process as claimed in claim 1 or claim 2, characterised in that the reactant gas flow further comprises an inert gas selected from gases including argon and/or helium.

Inventors: DUNFIELD JOHN S, TAYLOR BRADLEY J, DUNFIELD, JOHN S., TAYLOR, BRADLEY J.
Applicants: APPLIED MATERIALS INC, APPLIED MATERIALS, INC.
Application year: 1988
Main classification: H01L21
IPC codes: C23F4, H01L21