TWI505350B - Increasing masking layer etch rate and selectivity - Google Patents

Description

Mask layer etch rate and selectivity enhancement

The present application generally relates to the design of an etching process system and method using batch etching to increase the etch rate and selectivity of the mask layer etch.

Current methods for producing complementary metal oxide semiconductor (CMOS) transistors require a mask layer to separate and protect active device regions such as dielectrics, metal interconnects, strain, source/drain, and the like. . Due to the electrical and morphological similarity between tantalum nitride (Si ₃ N ₄ ) or tantalum oxide (SiOx, where x is greater than 0) and cerium oxide (SiO ₂ ), and because tantalum nitride is easily bonded to SiO ₂ It is often used as a mask layer. In general, tantalum nitride is used as an etch stop layer, but in certain cases, such as in a "dual damascene" process, tantalum nitride must be applied without changing the carefully controlled thickness of the ruthenium dioxide underlayer. Go eclipse. In this example, the etch selectivity of tantalum nitride to tantalum oxide (calculated as the tantalum nitride tantalum rate divided by the tantalum oxide etch rate) is desirably as high as possible to improve process margin (process margin) ). As the component continues to shrink, the thickness of the mask layer and the underlying layer shrinks. The etch selectivity of very thin layers will become even more challenging in the future.

Current techniques for selectively etching tantalum nitride can use different chemicals and methods. Both dry plasma etching and aqueous chemical etching are used for the removal of tantalum nitride. The aqueous chemical material may comprise diluted hydrofluoric acid (dHF), hydrofluoric acid/ethylene glycol, and phosphoric acid. The decision to use different chemicals is controlled by the etch rate of tantalum nitride and the need for bismuth oxide selectivity. Aqueous chemistry is preferred because of the reduced cost of ownership compared to dry technology. It is well known that the yttrium nitride etch rate in phosphoric acid is strongly affected by temperature, with the etch rate increasing in response to temperature rise. In a wet bench configuration such as immersing the substrate in a bath of aqueous phase phosphoric acid solution, the processing temperature is limited by the boiling point of the aqueous phase phosphoric acid solution. The boiling point of the solution is a function of the water concentration in the aqueous phosphoric acid solution and the atmospheric pressure. The current method for maintaining temperature is by a feedback loop controller that measures the presence of a boiling state, simultaneously adjusts the water volume of the bath and the heater power timing interval to boil this state. Maintained at the target temperature (typical range of target temperatures is from 140 degrees Celsius to 160 degrees Celsius). When the aqueous phosphoric acid solution is heated without the addition of water, the boiling point of the aqueous phosphoric acid solution rises as the water evaporates from the solution.

Since the current phosphoric acid recycle tank is utilized, increasing the phosphoric acid temperature at the expense of selectivity is advantageous for increasing the tantalum nitride etch rate and reducing the manufacturing cost for production, while allowing the high boiling point to result in a reduction in water concentration. Water is critical in controlling the selectivity of tantalum nitride for tantalum oxide or tantalum etching. Experimental evidence indicates that the non-boiling state at high temperatures (i.e., low water content) does not result in a suitable etch selectivity. Conversely, in order to improve the selectivity, it is preferred to have a high concentration of water (i.e., to further dilute the acid), but this is not practical. Increasing the water concentration in the bath reduces the boiling point of the acid mixture. At lower temperatures, the etch rate of tantalum nitride is significantly reduced due to the strong argon nitride etch rate and the temperature of the Arrhenius relationship.

In the prior art, for example, a method for controlling the etching rate of a tantalum oxide insulating layer in a boiling aqueous phase phosphoric acid solution for masking nitridation is disclosed in U.S. Patent No. 4,092,211.矽Insulation. This method employs the careful addition of the phthalate material to the boiling aqueous phase phosphoric acid solution. In addition, a method for continuously monitoring and controlling the composition of a low solids flux is disclosed in U.S. Patent No. 5,332,145, which utilizes a solvent having a specific gravity that closely matches the specific gravity of the flux composition. What is desired in the art is a method and system that maintains a high etch rate of the mask layer and also maintains high selectivity to the mask layer over 矽 or 矽 oxide. There is a need for batch etch processing systems and methods and single substrate systems and methods that meet the goals of etch rate, etch selectivity, etch time, and/or cost of ownership.

The present invention provides a method and system for increasing the etch rate and etch selectivity of a mask layer on each of a plurality of substrates, each of which has a layer of germanium or germanium oxide, wherein the system includes: An etching processing chamber for processing the plurality of substrates, the processing chamber containing a processing liquid for etching the mask layer; and a boiling device coupled to the processing chamber for generating a vapor water vapor mixture under high pressure Where, the vapor water vapor mixture is introduced into the processing chamber at a controlled rate to maintain a selected target etch rate and a target etch selectivity ratio of the mask layer to the tantalum or niobium oxide.

To assist in the description of the invention, a semiconductor substrate is used to illustrate the application of the concept. The method and process are equally applicable to other workpieces such as wafers, discs, or the like. Similarly, aqueous phase phosphoric acid is used to illustrate the treatment liquid in the present invention. Other treatment liquids can be selectively used as described below.

Referring to FIG. 1, an architectural diagram 10 illustrates a prior art method of etching tantalum nitride in a batch etch processing system in which an etch chemistry (etchant) is distributed to a plurality of substrates 26 using one or more input streams 34 and 38. The processing chamber 44 is etched. The etchant can be reused or recycled or disposed using the overflow tank 42 and the overflow port 18. Heater 22 can be provided, for example, by having a heater located at the side or bottom of processing chamber 44. The heater 22 can be in an external form or in an inline form.

2 depicts an exemplary architectural diagram of a prior art batch etch processing system 50 for etching tantalum nitride, including an etch processing chamber 66 and an overflow trench 58. As above, the heaters 70 can be disposed on the front, back, and underside of the etching process chamber 66; the heaters 70 can be external or pipelined and can provide an aqueous solution of heat flux 46 into the processing chamber 66. 94. The effluent heat flux comprises conduction 62 and evaporation of water 90. If the inflow heat flux is greater than the outflow heat flux due to evaporation and conduction, the temperature of the aqueous solution will increase until boiling occurs. The boiling point is determined by the acid concentration and atmospheric pressure. During boiling, the increase in heat causes the water to boil faster. To maintain the fixed boiling temperature of the aqueous solution 94, the processing chamber controller (not shown) must simultaneously adjust the heater 70 and the feed water 74 injected via the supply line 78. If the influent feed water is greater than the water loss caused by evaporation, the temperature of the aqueous solution drops, the acid is diluted, and the boiling point is lowered. On the other hand, if the inflow water is smaller than the water loss caused by evaporation, the temperature of the aqueous solution increases, the acid is concentrated, and the boiling point is raised.

It is well known that the cesium nitride etch rate in phosphoric acid is strongly affected by temperature, with the etch rate rising in response to temperature rise. The chemical reaction for etching tantalum nitride and etching ruthenium dioxide is as follows:

In a wet bench configuration, when the substrate is immersed in a bath of a water phase phosphoric acid solution (aqueous solution), for example, in the EXPEDIUS line of Tokyo Power Co., Ltd. (TEL), the treatment temperature is limited to the aqueous solution. Boiling point. The boiling point of an aqueous solution is a function of the concentration of water in the acid as a function of atmospheric pressure and can be described by the Clausius-Clapeyron relation and the Raoult's law. The Clausius-Clapeyron equation for the liquid-vapor boundary can be expressed as:

Where ln is the natural logarithm, T ₁ and P ₁ are the corresponding temperatures (expressed in Kelvins or other absolute temperature units) and vapor pressure, T ₂ and P ₂ are the corresponding temperatures and pressures at another point, △ H _Vap is a molar vaporization enthalpy, and R is a gas constant (8.314 J mol ^-1 K ^-1 ).

The law of pulling the ear indicates that the vapor pressure of the ideal solution depends on the vapor pressure of each chemical component and the molar fraction of the components present in the solution. Once the ingredients in the solution have reached equilibrium, the total vapor pressure p of the solution is:

And the individual vapor pressure of each component is Where: p _i is the partial pressure of component i in the mixture, p ^* _i is the vapor pressure of pure component i , and x _i is the molar fraction of component i in the solution (in the mixture).

An example of the equilibrium state of phosphoric acid and water is provided in Figure 5A. The current TEL EXPEDIUS system for maintaining temperature utilizes a feedback loop controller that measures boiling The presence of the state, the addition of the bath volume and the heater power timing interval are maintained to maintain the boiling state at the target temperature (160 ° C). When the aqueous solution is heated without adding water, the boiling point of the aqueous solution rises as the water evaporates from the solution.

Since the current phosphoric acid recycle tank is utilized, increasing the phosphoric acid temperature at the expense of selectivity is advantageous for increasing the tantalum nitride etch rate and reducing the manufacturing cost for production, while allowing the high boiling point to result in a reduction in water concentration. Water is critical in controlling the selectivity of tantalum nitride for SiO2 etching [chemical reactions in Equations 1, 2]. As shown in Figure 5B, experimental evidence indicates that the non-boiling state at high temperatures (i.e., low water content) does not result in a suitable etch selectivity. Conversely, in order to improve selectivity, it is preferred to have a high concentration of water (i.e., further dilute the acid); however, this is not practical. Increasing the water concentration in the bath reduces the boiling point of the aqueous solution. At lower temperatures, the etch rate of tantalum nitride is significantly reduced by the strong Arrhenius relationship between the tantalum nitride etch rate and temperature.

In order to emphasize that the solvent used may be water or some other solvent, the term "treatment liquid" will be used in the remainder of the specification. The present invention is directed to a novel method for increasing the transfer temperature of a liquid toward a tantalum nitride solution to increase the tantalum nitride etch rate while also maintaining a high water content to maintain optimum nitridation of germanium or germanium dioxide.矽 etch selectivity. The high temperature is achieved by injecting pressurized vapor into the flow of phosphoric acid prior to being dispensed onto a single substrate that is stationary or rotating. The condensation of vapor releases the latent thermal energy into the phosphoric acid, which provides efficient delivery to heat the phosphoric acid. The additional benefit for phosphoric acid is always automatically filled with water. Water is necessary to maintain high cerium nitride etch selectivity relative to cerium oxide. For unidirectional processing, phosphoric acid containing dissolved cerium oxide must be provided to aid in selective control. For recycling, dissolved cerium oxide is supplied in virgin phosphoric acid or by circulating a tantalum nitride cladding substrate through an etching process (this is a common treatment for batch etching systems, also known as phosphoric acid). Bath) and supply. In one embodiment, the vapor jet can also be used to preheat the substrate to ensure etch uniformity from the center to the edge on the substrate.

In particular, the problem addressed by the present invention is to improve the tantalum nitride etch rate process using a treatment liquid such as phosphoric acid to make single substrate processing practical and cost effective. Phosphoric acid treatment is typically considered a "dirty treatment" and is typically removed prior to the standard clean 1 (SC1) step to remove residual particulates. because The mechanism of defect/particle redeposition and/or backside to front side contamination can be avoided, so a single substrate etch process is essentially cleaner than batch etch. In the hot phosphoric acid at 160 ° C, the tantalum nitride etching treatment is slow (30-60 angstroms/min, or A/min). If the etch rate of tantalum nitride can be increased to more than 180 A/min, then the tantalum nitride treatment on a single substrate processing apparatus can be performed. In the case where direct vapor injection is used to heat the tantalum nitride, a high processing temperature can be achieved while maintaining the saturated water content required for the high tantalum nitride etch selectivity of tantalum or niobium dioxide.

In one embodiment, the boiling equipment (liquid water supplied to ambient temperature) is used to produce a supply of a high pressure vapor water vapor mixture. The temperature of the vapor water vapor mixture can be controlled by the pressure generated inside the boiler. The vaporous water vapor mixture is then transferred to a hot phosphoric acid chemical transfer line to a single substrate processing chamber. The vapor-vapor mixture will provide a source of heat and moisture to the bath, thereby raising the bath above the standard boiling temperature and introducing excess moisture that simultaneously exhibits a vapor phase and a liquid phase to maintain the relative cerium oxide and niobium nitride. Etching selectivity.

In another embodiment, the vapor water vapor mixture is combined with the treatment liquid under high pressure prior to entering the etching process chamber. Adequate pressure must be maintained to avoid boiling in the supply transfer line. Then, at the time of entering the etching process chamber of the surrounding pressure, the treatment liquid starts to boil rapidly. In another embodiment, a plurality of nozzles can be used above the substrate. The first nozzle introduces heated phosphoric acid; the second or more nozzles introduce a jet of high temperature vapor water vapor mixture to preheat the substrate surface prior to introduction of phosphoric acid to assist in maintaining a uniform temperature across the substrate, and thus ensure etch uniformity. In this embodiment, the nozzle position and the number of nozzles can be set to maximize the efficiency of heat transfer from the process liquid to the substrate. A vaporous water vapor mixture can also be injected onto the back side of the substrate to maintain temperature uniformity.

Figure 3 depicts an exemplary graph 300 of the boiling point of phosphoric acid as a function of phosphoric acid concentration and temperature at atmospheric pressure. The temperature and concentration of the treatment liquid are two key factors determining the etch rate and the cerium etch selectivity relative to the yttrium or lanthanum oxide. 3 depicts a boiling point curve 304 of the temperature of the batch etch process of tantalum nitride versus the concentration of phosphoric acid. Referring to boiling point curve 304, it is assumed that the treatment liquid is in condition A of the initial group labeled 312, for example, the treatment liquid has a weight percentage of 85 at about 120 degrees Celsius. Phosphoric acid concentration. The treatment liquid is heated until it reaches the boiling point, designated 308, as indicated by point X, which is the point in the boiling point curve 304 which also represents the control limit of the exemplary etch processing system. As described above, in order to increase the etching rate while maintaining the target tantalum nitride etch selectivity and maintaining the etching uniformity, the temperature of the processing liquid is increased.

4A is an exemplary graph 400 comprising a boiling point curve 404 for phosphoric acid (shown on the left vertical axis) and a vapor pressure curve 408 (shown on the right vertical axis), the boiling point curve 404 being a function of the concentration of phosphoric acid at atmospheric pressure, The vapor pressure curve 408 is a function of the temperature of the equilibrium condition of the mixture in the etching process system. The phosphoric acid concentration is expressed as a weight percentage of phosphoric acid in an aqueous solution. It is assumed that the initial condition of one of the treatment liquids is at a point (1) indicated by a dot corresponding to a temperature of 85% by weight of phosphoric acid and a temperature of 120 degrees Celsius (C). The treatment liquid is heated and reaches the boiling temperature indicated by the dashed line portion of the boiling point curve 404. Heating can be by using a line or external heater or by injecting a vaporous water vapor mixture onto the etch processing liquid. In one embodiment, the etch processing system has a limit high temperature represented by a corresponding temperature of 160 ° C as at point (2) on the boiling point curve 404. The combination of vapor and water vapor (vapor vapour mixture) is pumped into the bottom of the etching process until the treated liquid reaches a composition substantially corresponding to 92% by weight phosphoric acid, a temperature of 180 ° C, and about 1.0 MPa (MPa) ) The point of vapor pressure (3). Other combinations of vapor vapour mixture with aqueous phosphoric acid can be tested to determine the etch rate and etch selectivity of the tantalum nitride that meets the application target. The pressure of the vapor water vapor mixture can range from 0.2 to 2.0 MPa.

Referring to Figure 4B, it is assumed that a pressure of 0.5 MPa is selected as the target pressure of the vapor-vapor mixture. The corresponding temperature of the mixture (point A on vapor pressure curve 408) was about 152 °C. When the vaporous water vapor mixture is injected onto the treatment liquid in the dip bath or single substrate etching processing system, the boiling point is determined by the vertical line connecting point A to point A' of boiling point curve 404, resulting in a corresponding 86% correspondence at equilibrium. Phosphoric acid concentration. If the selected target pressure is 2.0 MPa, the corresponding temperature of the mixture (point B on vapor pressure curve 408) is about 214 °C. In the same manner, the boiling point is determined by the vertical line connecting point B to point B' of boiling point curve 404, resulting in a corresponding phosphoric acid concentration of about 96% at equilibrium. Therefore, the flow rate and pressure of the vapor water vapor mixture can be used as a variable for controlling the temperature of the treatment liquid, which affects the boiling temperature of the treatment liquid, and further determines The concentration of phosphoric acid in the liquid. The equilibrium phosphoric acid concentration and temperature of the treatment liquid affect the etch rate and etch selectivity.

Figure 5A depicts an exemplary graph 500 of a first curve 504 comprising a composition of a phosphoric acid solution and a second curve 508 of water, wherein the composition of the phosphoric acid solution is expressed as water phase molars per cubic meter (Aq. mols/m3 ^). And the water system is a function of the temperature presented in °C and is expressed as mols/m ³ . When the treatment liquid is heated in the range of 160 to 220 ° C, the phosphoric acid concentration is substantially constant, whereas the water concentration is lowered due to evaporation with increasing temperature. To further illustrate the change in etch selectivity of the treatment liquid, FIG. 5B depicts an exemplary graph 550 of etch selectivity of the phosphoric acid solution as a function of time and temperature of the treatment liquid in the etch processing system. At the beginning of the test, the treatment liquid (aqueous phase phosphoric acid) boils, and deionized water (DIW) is used to incorporate the treatment liquid, and the etch selectivity of the tantalum nitride to the cerium oxide is 554. After 50 minutes, the DIW incorporation was stopped and the temperature of the treatment liquid reached its apex at about 220 ° C, reaching a temperature substantially the same as before the heater power was reduced and before the temperature was lowered. As can be seen from the downward slope of the etch selectivity curve 564, the etch selectivity also decreases from high to low (554 to 558). After reinjecting the treatment liquid with DIW, the treatment liquid enters a boiling state and the etch selectivity rises from low to high (558 to 562). The inventors have found that the treatment liquid is useful for treating liquids using aqueous phase phosphoric acid in the range of from 160 to 200 ° C, and is preferably about 180 ° C.

FIG. 6A depicts an exemplary schematic diagram of a batch etch processing system 600 in accordance with an embodiment of the present invention. A plurality of substrates 632 are disposed in the etching process chamber 640. The treatment liquid 628 is introduced into the etching process chamber 640, and the excess process liquid enters the overflow container 604 and can be disposed via the discharge port 608. Vapor generator 614 supplies input liquid via transfer line 620 and is heated by heater 616 that produces vapor water vapor mixture 612. Vapor vapor mixture 612 is dispensed onto the bottom of etch processing chamber 640 by a via 636. In the case of a controller (not shown), the batch etch processing system 600 is configured to satisfy the selected flow rate by controlling the flow rate of the process liquid 628 and the vapor water vapor mixture 612 (either pressurized or not pressurized to high pressure). Etching process rate and selected etch selectivity ratio. The pressure of the vapor water vapor mixture can range from 0.2 to 2.0 MPa.

FIG. 6B depicts an exemplary schematic diagram of a single substrate etch processing system 650 in accordance with an embodiment of the present invention. A single substrate 654 is mounted on a platform 662 that is configured to maintain substrate 654 stationary or rotate substrate 654 as processing liquid 678 is dispensed from supply line 682 and vapor water vapor mixture 674 is dispensed from supply transfer line 670. . Vapor vapor mixture 674 is conveyed through supply transfer line 670 across susceptor 654 via nozzles 666 arranged to achieve uniform processing over the range of substrate 654. A plurality of etch processing systems similar to single substrate processing system 650 can be configured, for example, in a stacked, orthogonal, or circular arrangement and in a number of similar arrangements for use with a general substrate transfer system. Vapor may be delivered to the back side of substrate 654 via vapor transfer line 658 to preheat or maintain a uniform temperature across the range of substrate 654.

7A is an exemplary schematic diagram of a batch etch processing system 700 that uses a nozzle 730 to dispense a vaporous water vapor mixture, in accordance with an embodiment of the present invention. The treatment liquid 738 can be heated by a heater 716 disposed in the front and back of the etching process chamber 742. The heater 716 can be in an external form or in a pipeline form that supplies an inflow heat flux 720 to the process liquid 738 in the etch process chamber 742. Again, the additional inflow heat flux 722 is provided by the injection of vapor vapour mixture 736 in the process liquid 738 via the supply transfer line 726. The effluent heat flux comprises conduction 708 and water evaporation 734. If the inflow heat flux is greater than the outflow heat flux 708, 734 due to evaporation and conduction, the temperature of the treatment liquid 738 will increase until boiling occurs. The boiling point is determined by the concentration of the treatment liquid 738 and the atmospheric pressure. During boiling, the increase in heat will cause the water to boil faster.

To maintain a fixed boiling temperature of the process liquid 738, the process chamber controller (not shown) must simultaneously adjust the injection of the heater 716 and the vapor water vapor mixture via the nozzle 730. If the supply of the vapor water vapor mixture is greater than the water loss due to evaporation, the temperature of the treatment liquid 738 is reduced, the treatment liquid 738 is diluted, and the boiling point is lowered. Conversely, if the influent feed water is less than the water loss due to evaporation, the temperature of the treatment liquid 738 increases, the acid is concentrated, and the boiling point is increased. Placement of nozzle 730 at the bottom of etch processing chamber 742 provides a mixing effect to produce a uniform temperature distribution in process liquid 738. Process liquid 738 can be directed to nozzle 730 via second supply delivery line 724. Excessive treatment solution Body 738 flows to overflow trough 704. The batch etch processing system 700 is used to increase the etch rate of a mask layer such as tantalum nitride by increasing the temperature of the processing liquid 738. The target etch selectivity, i.e., the ratio of tantalum nitride etch to tantalum oxide or tantalum, is also maintained by controlling the molar concentration of the treatment liquid 738, such as by adding a slight vapor vapor mixture, and/or increasing or decreasing via The temperature of the vapor vapour mixture dispensed by nozzle 730.

FIG. 7B depicts an exemplary schematic diagram of a single substrate etch processing system 760 including a process liquid recovery system 783, in accordance with an embodiment of the present invention. As will be discussed further below, by maintaining a high concentration of dissolved cerium oxide in the treatment liquid to maintain the equilibrium of reaction 2 to the left, recovery treatment liquid 774 reduces the amount of chemicals and assists in etch selectivity. Referring to a single substrate etch processing system 760, a single substrate 796 is disposed on a platform 788 for restoring or rotating the substrate 796 within the etch processing chamber 762. Vapor vapor mixture 766 is delivered using supply line 764 and dispensed onto the substrate using nozzle 790. Vapor 769 is dispensed onto the back side of substrate 796 using vapor input line 768 to maintain a uniform temperature of substrate 796. Vapor 769 can be the same as vapor vapour mixture 766. The process liquid recovery system 783 includes a discharge line 786 coupled to the bottom of the etch process chamber 762 and through a control valve 782 that excludes a portion of the process liquid 774 via the purge line 780 and recovers the process liquid 774 via the recovery line 784. The rest of the. A selective heater 778 can be placed before or after processing the liquid transfer line 776 to maintain the desired temperature of the recovered process liquid 774. The new process liquid 774 is directed to a recovery line 784 using a process liquid transfer line 776.

Referring to FIG. 7B, the dissolved cerium oxide assists in maintaining the target cerium nitride etch rate by suppressing the reaction 2. In one embodiment, the dissolved cerium oxide (Si(OH) ₄ ) 770 is injected into the treatment liquid 774 using a cerium oxide injection line 772 and using a transfer line 776, and the amount of dissolved cerium oxide injected is sufficient. The amount of dissolved cerium oxide is maintained within a certain target range, for example, 10 to 30 ppm of dissolved cerium oxide. In one embodiment, the dissolved cerium oxide can be 20 ppm. In another embodiment, a plurality of substrates 796 containing tantalum nitride are treated to obtain a desired amount of dissolved cerium oxide in the recovered treatment liquid 774. One of the advantages of the present invention using a single substrate processing system is the resistance to higher concentrations of dissolved cerium oxide in the treatment liquid. Prior art batch etch processing systems using phosphoric acid typically exhibit an increase in the rate of enthalpy as the dissolved cerium oxide concentration increases. In addition to assisting in maintaining the resistance of the mask layer to a higher concentration of cerium oxide in a stable selectivity ratio of cerium oxide, a single substrate processing system is low due to the low enthalpy rate of the batch etch processing system for the same application. Essentially has an advantage.

8A, 8B, and 8C are exemplary schematic views of a transport system for an etch processing system in various embodiments of the present invention. In accordance with an embodiment, FIG. 8A depicts a processing system 800 for performing a non-plasma cleaning process on a substrate or a plurality of substrates. Processing system 800 includes a first processing system 816 and a second processing system 812 coupled to first processing system 816. For example, the first processing system 816 can include a chemical processing system (or a chemical processing component of a single processing chamber), and the second processing system 812 can include a thermal processing system (or a heat treatment component of a single processing chamber).

Furthermore, as shown in FIG. 8A, a transport system 808 can be coupled to the first processing system 816 for transporting a substrate or plurality of substrates into and out of the first processing system 816 and the second processing system 812, and with the multi-component manufacturing system. 804 exchange substrate. The first and second processing systems 816, 812 and the delivery system 808 can, for example, comprise processing elements within the multi-element manufacturing system 804. For example, multi-element fabrication system 804 can permit the transfer of a substrate or a plurality of substrates to and from processing elements, including devices such as etching processing systems, deposition systems, coating systems, patterning systems, metrology systems, and the like. In order to isolate the processing occurring in the first and second systems, isolation assembly 820 can be used to couple the various systems. For example, the isolation assembly 820 can include at least one of a thermal insulation assembly that provides thermal insulation and a gate valve assembly that provides vacuum isolation. Of course, processing systems 816 and 812 and delivery system 808 can be arranged in any order.

Alternatively, in another embodiment, FIG. 8B presents a processing system 850 to perform a non-plasma cleaning process on a substrate. Processing system 850 includes a first processing system 856 and a second processing system 858. For example, the first processing system 856 can include a chemical processing system and the second processing system 858 can include a thermal processing system.

Moreover, as shown in FIG. 8B, the transport system 854 can be coupled to the first processing system 856 to transport a substrate or plurality of substrates into and out of the first processing system 856, and A second processing system 858 can be coupled to transfer a substrate or plurality of substrates into and out of the second processing system 858. Additionally, transport system 854 can exchange one or more substrates with one or more substrate cassettes (not shown). Although only two processing systems are shown in FIG. 8B, other processing systems may still access the delivery system 854, including devices such as etching processing systems, deposition systems, coating systems, patterning systems, metrology systems, and the like. In order to isolate the processing occurring in the first and second systems, isolation assembly 862 can be used to couple the various systems. For example, the isolation component 862 can include at least one of a thermal insulation component that provides thermal insulation and a gate valve component that provides vacuum isolation. Further, for example, delivery system 854 can be part of isolation component 862.

Alternatively, in another embodiment, FIG. 8C presents a processing system 870 for performing a non-plasma cleaning process on a substrate or a plurality of substrates. Processing system 870 includes a first processing system 886 and a second processing system 882, wherein first processing system 886 is stacked on top of second processing system 882 as shown in the vertical direction. For example, the first processing system 886 can include a chemical processing system and the second processing system 882 can include a thermal processing system.

Furthermore, as shown in FIG. 8C, a transport system 878 can be coupled to the first processing system 886 to transport a substrate or plurality of substrates into and out of the first processing system 886 and to the second processing system 882 to The substrate or plurality of substrates are transferred into and out of the second processing system 882. Additionally, transport system 878 can exchange one or more substrates with one or more substrates (not shown). Although only two processing systems are shown in FIG. 8C, other processing systems may still access the transport system 878, including devices such as etching processing systems, deposition systems, coating systems, patterning systems, metrology systems, and the like. In order to isolate the processing occurring in the first and second systems, isolation component 874 can be used to couple the various systems. For example, the isolation assembly 874 can include at least one of a thermal insulation assembly that provides thermal insulation and a gate valve assembly that provides vacuum isolation. Further, for example, delivery system 878 can be part of isolation component 874. As noted above, the chemical processing system and the thermal processing system can include individual processing chambers coupled to one another. Alternatively, the chemical processing system and the thermal processing system can be a single processing chamber component.

9 is an etch rate and etching of a mask layer for use in a substrate for a batch etching process using a process liquid and a vapor-vapor mixture in one embodiment. An exemplary flow chart of the alternative method 900. In step 904, the target etch rate and the target etch selectivity ratio of the mask layer to tantalum oxide or germanium are selected. The mask layer can be tantalum nitride, gallium nitride, or aluminum nitride, and the like. In step 908, a supply of vapor water vapor mixture at high pressure is obtained. The vapor water vapor mixture may be provided by a vapor generator on the line or from a common vapor source in the manufacturing cluster. In step 912, a supply of process liquid to selectively etch the mask layer is obtained. The treatment liquid may comprise phosphoric acid, hydrofluoric acid, or hydrofluoric acid/ethylene glycol and the like. In step 916, the plurality of substrates are placed in an etch processing chamber. In step 920, the treatment fluid system is dispensed in an etch processing chamber, wherein dispensing can be performed using a supply delivery line or using a nozzle. In step 924, a flow of the vapor water vapor mixture is injected into the etching process chamber, wherein the flow rate of the vapor water vapor mixture is controlled to achieve a target etching rate of the mask layer and a target etching option of the mask layer for the tantalum oxide or tantalum. Sex. As shown in Figures 4A and 4B, the flow rate of the vapor water vapor mixture can be correlated with data based on the concentration of the treatment liquid, the temperature of the aqueous solution, and the vapor pressure. As mentioned in the description of Figure 4B, the flow rate and pressure of the vapor-vapor mixture can be used as a variable to control the temperature of the treatment liquid, which affects the boiling temperature of the treatment liquid and further determines the concentration of phosphoric acid in the treatment liquid. The equilibrium phosphoric acid concentration and temperature affect the etch rate and etch selectivity.

10 is an exemplary flow diagram of a method 1000 for increasing the etch rate and etch selectivity of a mask layer of a substrate in a batch etch processing system using a combined process liquid and vapor water vapor mixture. In step 1004, the target etch rate and the target etch selectivity of the mask layer for the tantalum oxide or germanium are selected. The mask layer can be tantalum nitride, gallium nitride, or aluminum nitride, and the like. In step 1008, a supply of vapor water vapor mixture at high pressure is obtained. The supply can be provided by a steam generator on the pipeline or from a common vapor source in the manufacturing cluster. In step 1012, a supply of process liquid to selectively etch the mask layer is obtained. The treatment liquid may comprise phosphoric acid, hydrofluoric acid, or hydrofluoric acid/ethylene glycol and the like. In step 1016, a plurality of substrates are placed in an etch processing chamber. In step 1020, the treatment fluid system is combined with the vapor water vapor mixture in a mixing tank or supply transfer line. Sufficient pressure must be maintained to avoid boiling in the supply transfer line. Upon entering the etching process chamber at ambient pressure, the process liquid will begin to boil rapidly.

Referring to FIG. 10, in step 1024, the combined vapor-vapor mixture and the flow of the treatment liquid are injected into the etching processing chamber, wherein the flow rate of the vapor-vapor mixture is controlled to achieve a target etching rate of the mask layer and a mask layer pair. The target etch selectivity of cerium oxide or cerium. As described above, the flow rate of the vapor water vapor mixture can be related to the data based on the treatment liquid concentration, the aqueous solution temperature, and the vapor pressure as shown in Figs. 4A and 4B. As mentioned in the description of Figure 4B, the flow rate and pressure of the vapor-vapor mixture can be used as a variable to control the temperature of the treatment liquid, which affects the boiling temperature of the treatment liquid and further determines the concentration of phosphoric acid in the treatment liquid. The equilibrium phosphoric acid concentration and temperature affect the etch rate and etch selectivity.

Correlation can be used to determine the flow rate required to meet the target etch rate and target etch selectivity. In one embodiment, the vapor water vapor mixture and treatment fluid system are combined in a supply delivery line prior to entering the etching process chamber. In another embodiment, the vapor water vapor mixture and the treatment liquid are combined prior to exiting the supply delivery line in the discharge etch processing chamber.

11 is an exemplary flow diagram of a method 1100 of increasing the etch rate and etch selectivity of a mask layer of a substrate in a batch etch processing system using a plurality of nozzles disposed at the bottom and sides of the etch processing chamber. In step 1104, the target etch rate and the target etch selectivity of the mask layer for the tantalum oxide or germanium are selected. The mask layer can be tantalum nitride, gallium nitride, or aluminum nitride, and the like. In step 1108, a supply of vapor water vapor mixture at high pressure is obtained. The supply can be provided by a steam generator on the pipeline or from a common vapor source in the manufacturing cluster. In step 1112, a supply of processing liquid to selectively etch the mask layer is obtained. The treatment liquid may comprise phosphoric acid, hydrofluoric acid, or hydrofluoric acid/ethylene glycol and the like. In step 1116, the plurality of substrates are placed in an etch processing chamber. In step 1120, the treatment fluid system is dispensed in an etch processing chamber.

In step 1124, the combined vapor vapour mixture and the flow of the treatment liquid are injected into the etching process chamber using a plurality of nozzles, wherein the flow rate of the vapor vapour mixture is controlled to achieve a target etch rate of the mask layer and a mask layer confrontation. The target etch selectivity of the oxide or germanium. Multiple nozzles can be placed in the bottom and/or side of the etch processing chamber. The configuration of the multiple nozzles can be changed to ensure uniform temperature Sexual and subsequent etching uniformity. As described above, the flow rate of the vapor water vapor mixture can be related to the data based on the treatment liquid concentration, the aqueous solution temperature, and the vapor pressure as shown in Figs. 4A and 4B. As described in the description of Figure 4B, the flow rate and pressure of the vapor water vapor mixture can be used as a variable to control the temperature of the treatment liquid, which affects the boiling temperature of the treatment liquid and further determines the concentration of phosphoric acid in the treatment liquid. The equilibrium phosphoric acid concentration and temperature affect the etch rate and etch selectivity.

12 is an exemplary flow diagram of a method 1200 of adding an etch rate and etch selectivity of a substrate in a single substrate etch processing system. In step 1204, the target etch rate and the target etch selectivity of the mask layer for the tantalum oxide or germanium, and/or target completion time are selected. The mask layer can be tantalum nitride, gallium nitride, or aluminum nitride, and the like. In step 1208, a supply of vapor water vapor mixture at high pressure is obtained. The supply can be provided by a steam generator on the pipeline or from a common vapor source in the manufacturing cluster. In step 1212, a supply of processing liquid to selectively etch the mask layer is obtained. The treatment liquid may comprise phosphoric acid, hydrofluoric acid, or hydrofluoric acid/ethylene glycol and the like. In step 1216, a single substrate is placed in the etch processing chamber. In an embodiment, two or more etch processing chambers may be configured such that the chambers are subject to a supply of processing liquid, a supply of vaporized water vapor mixture, and loading and unloading of substrates. In step 1220, the treatment fluid system is dispensed in an etch processing chamber, wherein the dispensing can be performed using a supply delivery line or nozzle. In step 1224, the vapor water vapor mixture and/or the flow of the treatment liquid is injected into the etching process chamber using one or more nozzles as the substrate rotates. Alternatively, the substrate can be stationary while the nozzle is being rotated.

Referring to Figure 12, in one embodiment, the process liquid and vapor water vapor mixture are combined in a supply transfer line prior to entering the etch processing chamber or after entering the etch processing chamber but before exiting the nozzle. Adequate pressure must be maintained to prevent boiling in the supply line. The process liquid will then begin to boil rapidly as it enters the processing chamber of ambient pressure. In another embodiment, a plurality of nozzles can be used above the substrate. The first nozzle introduces heated phosphoric acid, and the second or more nozzles introduce a jet of high temperature vapor to preheat the substrate surface prior to introduction of phosphoric acid to assist in maintaining a uniform temperature across the substrate and ensuring etch uniformity. In another embodiment, the nozzle position and the number of nozzles can be set such that the heat transfer efficiency from the treatment liquid to the substrate is maximized. Big. In yet another embodiment, a vaporous water vapor mixture can also be injected onto the back side of the substrate to maintain temperature uniformity.

Figure 13 is an exemplary block diagram of a system 1300 for determining and utilizing contour parameters of structures on a substrate after etching, wherein contour parameter values are used for automated processing and device control. System 1300 includes a first manufacturing cluster 1302 and an optical metrology system 1304. System 1300 also includes a second manufacturing cluster 1306. For details of the optical measurement system for determining the profile parameters of the structure on the substrate, reference is made to GENERATION OF A LIBRARY OF PERIODIC GRATING DIFFRACTION SIGNALS of US Pat. No. 6,943,900, issued Sep. 13, 2005, the entire disclosure of which is incorporated herein by reference. . Although the second manufacturing cluster 1306 is depicted in FIG. 13 as being after the first manufacturing cluster 1302, it should be noted that, for example, in the manufacturing process flow, the second manufacturing cluster 1306 can be located in the system 1300 before the first manufacturing cluster 1302. .

For example, photolithographic processing that exposes and/or develops the photoresist layer applied to the substrate can be performed using the first fabrication cluster 1302. In an exemplary embodiment, optical metrology system 1304 includes an optical metrology tool 1308 and a processor 1310. Optical metrology tool 1308 is configured to measure a diffracted signal exiting the sample structure. The processor 1310 is configured to: modulate the diffracted signal measured by the optical metrology tool and use the signal conditioner to adjust and generate the adjusted measurement output signal. Moreover, the processor 1310 is configured to compare the adjusted measurement output signal to the analog diffracted signal. As described above, the simulated diffraction system is determined using an optical metrology tool model that uses ray tracing, contour parameters of a set of structures, and numerical analysis of the Maxwell equation based on electromagnetic diffraction. In an exemplary embodiment, optical metrology system 1304 can also include a library 1312 having complex analog diffracted signals and complex values of one or more contour parameters associated with the complex analog diffracted signals. As described above, the library can be generated by the line; the measurement processor 1310 can compare the adjusted measurement output signal with the complex analog diffraction signal in the library. When a matching analog diffract signal is found, one or more of the contour parameters associated with the matched analog diffract signal in the library are assumed to be one or more of the contour parameters used in the substrate application. To make a sample structure.

System 1300 also includes a measurement processor 1316. In an exemplary embodiment, The processor 1310 can communicate one or more values of one or more profile parameters to the measurement processor 1316. The measurement processor 1316 can then adjust one or more processing parameters or device settings of the first manufacturing cluster 1302 based on one or more values of one or more profile parameters determined using the optical metrology system 1304. The measurement processor 1316 can also adjust one or more processing parameters or device settings of the second manufacturing cluster 1306 based on one or more values of one or more profile parameters determined using the optical metrology system 1304. As described above, the second fabrication cluster 1306 can process the substrate before or after the first fabrication cluster 1302. In another exemplary embodiment, processor 1310 is configured to adjust the machine using the set of measured diffracted signals as input to machine learning system 1314 and using profile parameters as desired output of machine learning system 1314. Learning system 1314.

14 is an exemplary flow diagram of a method of controlling fabrication clusters using an etch processing system configured to increase etch rate and etch selectivity. In the case of using the system described in FIG. 13, after etching using the systems and methods described with respect to Figures 3 through 12, the structures in the substrate can be used, such as determining and utilizing contour parameters of automatic processing and device control. The method depicted by the exemplary block diagram 1400 of the system is measured. In step 1410, the measurement diffraction signal exiting the sample structure is obtained using an optical metrology tool. In step 1420, the measurement output signal is measured by a ray tracing method, an optical measurement device calibration parameter, and one or more accuracy criteria or other scattering methods such as regression, library matching, or machine learning systems. The radio signal is judged. In step 1430, at least one profile parameter of the sample structure is determined using the measured output signal. In step 1440, at least one manufacturing process parameter or device setting is modified using at least one profile parameter of the structure.

Referring to Figures 6A and 6B, a controller (not shown) can be used to control the flow rate of the process liquid and vapor-vapor mixture in a batch or single substrate etching application, the pressure of the process liquid, and the order in which the nozzles are used. The program stored in the memory of the controller can be used to initiate input to the components of the aforementioned etch processing system 600, 650 (Figs. 6A and 6B) in accordance with the processing recipe to perform an increased etch rate and a mask layer compared to 矽 or 矽A method of etching selectivity of an oxide. One example of controller 1090 is DELL PRECISION WORKSTATION available from Dell Corporation of Austin, Texas. 610TM. The controller can be localized with respect to the etch processing system 600, 650, or it can be remotely located via the internet or internal network associated with the etch processing systems 600, 650. Thus, the controller can exchange data with the etch processing systems 600, 650 using at least one of a direct connection, an internal network, or an internet. The controller can be coupled to an internal network (ie, device manufacturer, etc.) at the customer's location, or to an internal network (ie, device manufacturer) that is coupled to the supplier's location. Furthermore, another computer (ie, controller, server, etc.) can access the controllers of the etch processing system 600, 650 to exchange data via at least one of a direct connection, an internal network, or the Internet.

Although the exemplary embodiments have been described, various modifications may be made without departing from the spirit and scope of the invention. For example, the invention is illustrated and described using etching of a mask layer on a substrate, specifically tantalum nitride. Other masking materials or insulating layers can be treated using the same methods and systems as described in the specification. Therefore, the present invention should not be construed as limited to the particular forms shown in the drawings. Accordingly, all such modifications are intended to be included within the scope of the invention.

10‧‧‧Architecture

18‧‧‧Overflow

22‧‧‧heater

26‧‧‧Multiple substrates

34‧‧‧Input Vapor

38‧‧‧Input Vapor

42‧‧‧Overflow trough

44‧‧‧Processing chamber

46‧‧‧Inflow of heat flux

50‧‧‧Batch etching system

58‧‧‧Overflow trough

62‧‧‧ Conduction

66‧‧‧Processing chamber

70‧‧‧heater

74‧‧‧Water supply

78‧‧‧Supply pipeline

90‧‧‧Water evaporation

94‧‧‧ aqueous solution

300‧‧‧ Chart

304‧‧‧ boiling point curve

308‧‧‧ boiling point

312‧‧‧Condition A

400‧‧‧ Chart

404‧‧‧ boiling point curve

408‧‧‧Vapor pressure curve

500‧‧‧ Chart

504‧‧‧First curve

508‧‧‧second curve

550‧‧‧ Chart

554‧‧‧High etching selectivity

558‧‧‧Low etch selectivity

562‧‧‧High etching selectivity

564‧‧‧etching selectivity curve

600‧‧‧etching system

604‧‧‧Overflow container

608‧‧‧Export

612‧‧‧Vapor vapour mixture

614‧‧‧Vapor generator

616‧‧‧heater

620‧‧‧Transport line

628‧‧‧Processing liquid

632‧‧‧Substrate

636‧‧‧ take over

640‧‧‧etching chamber

650‧‧‧Processing system

654‧‧‧Substrate

658‧‧‧Vapor transfer line

662‧‧‧ platform

666‧‧‧Nozzle

670‧‧‧Supply transfer line

674‧‧‧Vapor vapour mixture

678‧‧‧Processing liquid

682‧‧‧Supply pipeline

700‧‧‧Batch etching system

704‧‧‧Overflow trough

708‧‧‧ Conduction

716‧‧‧heater

720‧‧‧ inflow heat flux

722‧‧‧Additional inflow heat flux

724‧‧‧Second supply transfer line

726‧‧‧Supply transfer line

730‧‧‧Nozzle

734‧‧‧Water evaporation

736‧‧‧Vapor vapour mixture

738‧‧‧Processing liquid

742‧‧‧etching chamber

760‧‧‧Single substrate etching processing system

762‧‧‧etching chamber

764‧‧‧Supply pipeline

766‧‧‧Vapor vapour mixture

768‧‧‧Vapor input line

769‧‧‧Vapor

770‧‧‧dissolved cerium oxide

772‧‧‧2O2 injection line

774‧‧‧Processing liquid

776‧‧‧Transportation pipeline

778‧‧‧heater

780‧‧ ‧excluding pipeline

782‧‧‧Control valve

783‧‧‧Processing liquid recovery system

784‧‧‧Recycling pipeline

786‧‧‧Drainage line

788‧‧‧ platform

790‧‧‧Nozzles

796‧‧‧Substrate

800‧‧‧Processing system

804‧‧‧Multi-component manufacturing system

808‧‧‧Transport system

812‧‧‧Second treatment system

816‧‧‧First Processing System

820‧‧‧Isolation components

850‧‧‧Processing system

854‧‧‧Transport system

856‧‧‧First Processing System

858‧‧‧Second treatment system

862‧‧‧Isolation components

870‧‧‧Processing system

874‧‧‧Isolation components

878‧‧‧Transport system

882‧‧‧Second treatment system

886‧‧‧First Processing System

900‧‧‧ method

904‧‧‧Steps

908‧‧‧Steps

912‧‧ steps

916‧‧‧Steps

920‧‧‧Steps

924‧‧‧Steps

1000‧‧‧ method

1004‧‧‧Steps

1008‧‧‧Steps

1012‧‧‧Steps

1016‧‧‧Steps

1020‧‧‧Steps

1024‧‧‧ steps

1100‧‧‧ method

1104‧‧‧Steps

1108‧‧‧Steps

1112‧‧‧Steps

1116‧‧‧Steps

1120‧‧‧Steps

1124‧‧‧Steps

1200‧‧‧ method

1204‧‧‧Steps

1208‧‧‧Steps

1212‧‧‧Steps

1216‧‧‧Steps

1224‧‧‧Steps

1300‧‧‧ system

1302‧‧‧First Manufacturing Cluster

1304‧‧‧Optical measurement system

1306‧‧‧Second Manufacturing Cluster

1308‧‧‧Optical measuring tools

1310‧‧‧ processor

1312‧‧‧Library

1314‧‧‧ Machine Learning System

1316‧‧‧Measurement processor

1400‧‧‧block diagram

1410‧‧‧Steps

1420‧‧‧Steps

1430‧‧‧Steps

1440‧‧‧Steps

1 is a block diagram showing a prior art method of etching tantalum nitride in a batch etching process.

2 depicts an exemplary architectural diagram showing a prior art batch etch processing system that uses feed water and a heater for etching tantalum nitride.

Figure 3 depicts an exemplary graph of the boiling point of phosphoric acid as a function of phosphoric acid concentration and temperature.

4A is an exemplary graph of the boiling point of phosphoric acid as a function of phosphoric acid concentration and temperature, and an exemplary graph of vapor pressure as a function of temperature as a mixture equilibrium condition in an etch processing system.

4B is an exemplary graph of the boiling point of phosphoric acid as a function of phosphoric acid concentration and temperature, and an exemplary graph of vapor pressure as a function of temperature of the equilibrium conditions of the mixture under two vapor pressures in an etch processing system.

Figure 5A depicts an exemplary graph of the composition of a phosphoric acid solution as a function of temperature.

Figure 5B depicts an exemplary graph of etch selectivity of a phosphoric acid solution as a function of time and temperature in an etch processing system.

6A depicts an exemplary schematic of a batch etch processing system in accordance with an embodiment of the present invention.

6B depicts an exemplary schematic diagram of a single substrate etch processing system in accordance with an embodiment of the present invention.

7A is an exemplary schematic diagram of a batch etch processing system that uses a nozzle to dispense vapor in accordance with an embodiment of the present invention.

7B depicts an exemplary schematic diagram of a single substrate etch processing system including a process liquid recovery system in accordance with an embodiment of the present invention.

8A, 8B, and 8C are exemplary schematic diagrams of a delivery system for an etch processing system in various embodiments of the present invention.

9 is an exemplary flow diagram of a method for increasing the etch rate and etch selectivity of a mask layer for a substrate for a batch etch processing system using a process liquid and vapor in one embodiment of the invention.

10 is an exemplary flow diagram of a method of using a combined process liquid and vapor to increase the etch rate and selectivity of a mask layer for a substrate of a batch etch processing system in one embodiment of the invention.

11 is an exemplary flow diagram of a method of using an injection nozzle to increase the etch rate and selectivity of a mask layer for a substrate of a batch etch processing system in one embodiment of the invention.

12 is an exemplary flow diagram of a method of increasing the etch rate and selectivity of a mask layer of a substrate in a single substrate etch processing system in accordance with an embodiment of the present invention.

13 is an exemplary schematic diagram of a process control system in an embodiment of the invention for controlling fabrication clusters using an etch processing system configured to increase etch rate and etch selectivity.

14 is an exemplary flow diagram of a method of controlling fabrication clusters using an etch processing system configured to increase etch rate and etch selectivity in one embodiment of the invention.

600‧‧‧etching system

604‧‧‧Overflow container

608‧‧‧Export

612‧‧‧Vapor vapour mixture

614‧‧‧Vapor generator

616‧‧‧heater

620‧‧‧Transport line

628‧‧‧Processing liquid

632‧‧‧Substrate

636‧‧‧ take over

640‧‧‧etching chamber

Claims (18)

A system for increasing the etch rate and etch selectivity of a mask layer on each of a plurality of substrates, each of the plurality of substrates having a layer of germanium or germanium oxide, the system comprising: an etching process chamber Configuring to process the plurality of substrates, the etch processing chamber containing processing liquid for etching the mask layer on the plurality of substrates; a boiling device coupled to the etch processing chamber and configured to generate vapor at high pressure a supply of a water vapor mixture; and a controller that controls the processing liquid flow rate, molar concentration, pressure, and temperature of the etching process to achieve a target etching rate, a target etching selectivity ratio, and a target etching completion time; wherein the vapor water vapor The mixture is introduced into the etching process chamber at a flow rate sufficient to maintain a selected target etch rate and a selected target etch selectivity ratio of the mask layer to the ruthenium or osmium oxide, wherein the vapor water vapor mixture and treatment at high pressure The liquid system is combined under high pressure before leaving the supply transfer line to the etching processing chamber, wherein the etching process is at a batch , And the processing system aqueous phosphoric acid solution phase. A system for increasing the etch rate and etch selectivity of a mask layer on each of a plurality of substrates, wherein the mask layer comprises tantalum nitride, gallium nitride, or aluminum nitride, as in claim 1 One of them. A system for increasing the etching rate and etching selectivity of a mask layer on each of a plurality of substrates, wherein the temperature of the aqueous phosphoric acid solution is in the range of 160 to 220 degrees Celsius. A system for increasing the etching rate and etching selectivity of a mask layer on each of a plurality of substrates, as in claim 2, wherein: the flow rate and pressure of the vapor water vapor mixture are controlled to maintain the selected The target etch rate and the target etch selectivity of the tantalum nitride selected for tantalum or niobium oxide. A system for increasing the etching rate and etching selectivity of a mask layer on each of a plurality of substrates, as in claim 1, wherein: the nozzles assembled along the bottom and sides of the etching processing chamber are used. Introducing the vaporous water vapor mixture at elevated pressure into the etch processing chamber; and introducing the vaporized water vapor mixture at a controlled rate to maintain the selected target etch rate and the mask layer's choice of tantalum or niobium oxide The target etches the selectivity ratio. A system for increasing the etching rate and etching selectivity of a mask layer on each of a plurality of substrates, as in claim 1, wherein the processing liquid comprises hydrofluoric acid or hydrofluoric acid/B. One of the diols. A system for increasing the etching rate and etching selectivity of a mask layer on each of a plurality of substrates, wherein the flow rate and pressure of the vapor water vapor mixture are controlled to produce the processing liquid, as in claim 1 The temperature, thus the boiling temperature of the treatment liquid, and the equilibrium concentration and temperature of the treatment liquid are further produced to achieve the target etch rate and the target etch selectivity ratio. A method for increasing an etch rate and an etch selectivity of a mask layer on each of a plurality of substrates, the method comprising: a substrate fabrication step of fabricating the plurality of substrates each comprising the mask layer and a layer of germanium or antimony oxide; a vapor-vapor mixture supply step of obtaining a supply of a vapor-vapor mixture at a pressure in the range of 0.2 to 2.0 megapascals (MPa); a process of supplying a liquid to obtain a supply of a treatment liquid for selectively at a target etch rate And etching a selective ratio of the target, etching the mask layer relative to the germanium or germanium oxide; a placing step of placing the plurality of substrates in the etching processing chamber; combining a step of combining the processing liquid with the vapor water vapor mixture; and an injecting step of injecting the combined processing liquid and the vaporous water vapor mixture into the etching processing chamber In the chamber; wherein the operating parameters of the etching process are controlled to achieve a target etching rate and a target etching selectivity ratio, and wherein the etching process is one batch processing, and the processing liquid system is an aqueous phase phosphoric acid solution. A method of increasing the etch rate and etch selectivity of a mask layer on each of a plurality of substrates, as in claim 8, wherein the mask layer comprises tantalum nitride. A method of increasing the etching rate and etching selectivity of a mask layer on each of a plurality of substrates, as in claim 9, wherein the temperature of the aqueous phosphoric acid solution is in the range of 160 to 180 degrees Celsius. A method of increasing the etching rate and etching selectivity of a mask layer on each of a plurality of substrates, as in claim 9, wherein the vapor water vapor mixture and the treatment are at a pressure ranging from 0.2 to 2.0 MPa The liquid system is combined prior to entering the etching process chamber. A method of increasing the etch rate and etch selectivity of a mask layer on each of a plurality of substrates, as in claim 9, wherein the implanting step is performed along the bottom and/or sides of the etch processing chamber An assembled nozzle; and the vaporous water vapor mixture is introduced at a controlled rate to maintain the target etch selectivity of tantalum nitride for tantalum or niobium oxide. A method of increasing the etching rate and etching selectivity of a mask layer on each of a plurality of substrates, as in claim 9, wherein the processing liquid package is substituted for phosphoric acid Containing one of hydrofluoric acid or hydrofluoric acid/ethylene glycol. A method of increasing an etch rate and an etch selectivity of a mask layer on each of a plurality of substrates according to claim 13 wherein the mask layer comprises one of tantalum nitride, gallium nitride, or aluminum nitride. By. A method of increasing the etching rate and etching selectivity of a mask layer on each of a plurality of substrates according to claim 14, wherein the flow rate and pressure of the vapor water vapor mixture are controlled to generate a temperature of the processing liquid, Thus, the boiling temperature of the treatment liquid is generated, and the equilibrium concentration and temperature of the treatment liquid are further generated to achieve the target etching rate and the target etching selectivity ratio. A method of increasing etching rate and selectivity on each of a plurality of etched substrates, the method comprising: placing each of the plurality of substrates including a cerium nitride mask layer and a layer of lanthanum or cerium oxide in an etch batch process Etching the processing chamber; combining the processing liquid with the vapor water vapor mixture at a pressure in the range of 0.2 to 2.0 MPa; and injecting the combined processing liquid and the vapor water vapor mixture into the etching processing chamber; The flow rate, molar concentration, temperature, and pressure of the treatment liquid and the vapor water vapor mixture are controlled to maintain a target etch rate of the tantalum nitride, a target etch selectivity ratio of the tantalum nitride to the tantalum or niobium oxide, And the target etching completion time. A method of increasing etching rate and selectivity on each of a plurality of substrates, as in claim 16, wherein the processing liquid does not comprise phosphoric acid, but comprises hydrofluoric acid, or hydrofluoric acid/ethylene glycol. One. Increasing the etch on each of the etched plurality of substrates as in claim 17 An engraving rate and selectivity method, wherein the flow rate and pressure of the vapor-vapor mixture are controlled to produce a temperature of the treatment liquid, thereby generating a boiling temperature, and further generating an equilibrium concentration and temperature of the treatment liquid to achieve the target etching Rate and the target etch selectivity ratio.