US20020176984A1 - Silicon penetration device with increased fracture toughness and method of fabrication - Google Patents

Abstract

A silicon penetration device with increased fracture toughness and method of fabrication thereof are provided. The method comprises strengthening silicon penetration devices by thermally growing a silicon oxide layer on the penetration device and then subsequently stripping the silicon oxide. The method also includes strengthening silicon penetration devices through the sputtering of thin film coatings on the silicon penetration devices.

Description

TECHNICAL FIELD
• This invention relates generally to a method for strengthening silicon penetration devices such as needles or probes by increasing fracture toughness.[0001]
BACKGROUND
• It is well known in the art that silicon is a brittle substance. A penetration device constructed from single crystal silicon must possess a certain degree of mechanical robustness in order to ensure successful use of the needle without accidental fracture of the needle in patients. The device may have an interior channel (a hollow penetration device through which fluids can pass for sampling or injection) or it may be solid (for use as a lancet or probe). Integrated circuit and MEMS (microelectromechanical systems) technologies are used to fabricate these silicon penetration devices. Common MEMS fabrication methods, such as bulk etching with potassium hydroxide solution, leave the surface of the penetration device in a roughened state, with resultant increase in surface flaws. The actual failure of the silicon penetration device is the result of microcrack propagation initiated at a flaw on the surface of the material. It is important therefore, to increase the fracture toughness of the penetration device to permit reliable skin penetration without breakage.[0002]
• In Kim et al, U.S. Statutory Invention Registration H001166, a tightly adherent thermally grown silicon containing oxide layer was utilized in order to limit the strength diminishing effects of microflaws located on the surface of the substrate. The materials applied are a composition of matter comprising silicon-based ceramics. In Kim, the material was exposed to an environment of essentially hydrogen and water vapor at the correct temperature and pressure for a predetermined amount of time thereby forming the oxide layer.[0003]
• In Leger et al, U.S. Pat. No. 3,628,983, thin film coatings were applied to vitreous and vitrocrystalline (derived from or consisting of glass) bodies. Chemical modifications were made to the coatings of Leger while the coatings were in a heated condition with the film and substrate being subsequently cooled to create compressive stresses in the films. The chemical modifications varied between a step involving the oxidation of a metal or a metal compound, and the replacement of alkali metal ions in the coating by ions which derived from the medium and which conferred on the coating a lower coefficient of thermal expansion. Creating a compressive stress on the surface of the substrate provides a means of holding together surface defects which otherwise limit the strength of the material.[0004]
• In Ishi et al, U.S. Pat. No. 4,985,368, the substrate of a semiconductor was strengthened by depositing oxide over a corner of the device. The substrate consisted of a main surface, a predetermined impurity concentration of a first conductivity type, and a trench with a sufficient radius of curvature over at least a bottom corner portion thereof. A two-layer film consisting of oxide and nitride was formed on the main surface of the substrate, the side portions of the trench and a portion of the bottom of the trench. A second, selective, oxide layer was formed on the bottom and at the corner portion of the trench. The selective oxide layer spanned the corner portion of the trench with a radius of curvature more than {fraction (1/10)} and less than ½ of the width of the trench.[0005]
• The above prior art teaches the application of oxide to produce a compressive film intended to reduce microcrack propagation. In no case was the film subsequently removed, providing the substantial increase in fracture toughness shown in our present invention.[0006]
• In Leger, an external thin film coating was applied to a material in an attempt to minimize the effects of surface flaws. However, Leger did not use nickel as one of the thin films. Furthermore, the materials that are being strengthened are vitreous and vitrocrystalline bodies. Also, the methods of Leger involve creating compressive stresses in the films through both chemical treating at an elevated temperature and subsequent cooling.[0007]
• In Wilson et al “Fracture Testing of Bulk Silicon Microcantilever Beams Subjected to a Side Load” silicon microcantilevers were fracture tested experimentally. However, the silicon microcantilevers of the Wilson experiment did not undergo surface modifications. Furthermore, in Wilson, the strengthening of devices through surface modifications was not addressed.[0008]
• While the prior art devices exemplify existing methods, there still exists a need for improved methods for strengthening silicon penetration devices by increasing fracture toughness.[0009]
SUMMARY
• It is an object of the present invention, therefore, to provide a strengthened silicon penetration device with increased fracture toughness and method for fabrication thereof. The penetration device or probe of such a device is approximately the thickness of a human hair, much smaller than a metal needle or lancet, yet can penetrate skin reliably and virtually painlessly.[0010]
• Another object of the present invention is to strengthen silicon penetration devices by thermally growing a silicon oxide layer on the penetration device or probe from the bulk silicon material thereof and subsequently stripping the silicon oxide therefrom.[0011]
• Yet another object of the present invention is to strengthen penetration devices through the sputtering of thin film coatings on the silicon penetration device or probe.[0012]
• Another object of the present invention is to provide silicon penetration devices on which a silicon oxide layer was thermally grown from the bulk silicon material of the device substrate and then subsequently removed, resulting in an increase in fracture toughness.[0013]
• Still another object of the present invention is to provide silicon penetration devices which are coated with a one (1) micrometer nickel film, resulting in an increase in fracture toughness.[0014]
• Another object of the present invention is to provide a method of increasing fracture toughness that does not require a film in a compressed state in the finished product.[0015]
• To achieve the foregoing and other objects and in accordance with the purpose of the present invention as embodied and broadly described herein, the present invention is directed to a penetration device with increased fracture toughness and method for its construction.[0016]
BRIEF DESCRIPTION OF THE DRAWINGS
• FIG. 1A is a sectional side view illustrating an unprocessed[0017]silicon penetration device10a,that is, the device prior to applying the methods of the present invention;
• FIG. 1B is a sectional side view illustrating a[0018]silicon penetration device10bafter formation of asilicon oxide layer12bon the top and bottom surfaces thereof;
• FIG. 1C is a sectional side view illustrating a[0019]silicon penetration device10cafter removal of the silicon oxide layer12cto expose the smoothed silicon surface; and
• FIG. 1D is a sectional side view illustrating a[0020]silicon penetration device10dhaving anickel film14ddeposited thereon.
• The first two digits of each reference number in the above figures indicate related elements. The third digit indicates the figure in which an element is shown.[0021]
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
• The present invention comprises methods of increasing the fracture toughness of silicon penetration devices. The first method comprises two steps. In the first step, the silicon surface of the device substrate is reacted at elevated temperatures with gaseous materials to form a thick adherent silicon-containing chemical film, for example a silicon oxide or oxynitride, on the silicon substrate surface. In the second step, the chemically-bound silicon film is removed by etching.[0022]
• FIG. 1A shows a side sectional view of[0023]silicon substrate10aof a previously unprocessed penetration device, that is, a device prior to applying the methods of this invention. The penetration device silicon has been fabricated using standard integrated circuit (IC) and microelectromechanical systems (MEMS) processing technologies, probably including wet etching.
• As illustrated in FIG. 1B, an embodiment of the present invention includes a method for strengthening silicon penetration devices by thermally growing a[0024]silicon oxide layer12bon siliconpenetration device substrate10b,and subsequently stripping thesilicon oxide layer12bfromsubstrate10b.Theresultant silicon substrate10c,which has a freshly exposed silicon surface, is illustrated in FIG. 1C. As illustrated in FIG. 1D, the present invention further includes strengthening penetration devices through the sputtering ofthin film coating14don thesilicon substrate10d.
• The first step is the thermal growing of a thin layer of[0025]silicon oxide12bon the surface of thesilicon substrate10aby oxidizing the bulk silicon of the substrate surface. The second step is the subsequent removal ofsilicon oxide layer12bin a buffered oxide etch. Each of these two processing steps results in penetration devices which exhibit an increase in the critical strength values (that is, the maximum bending force and maximum critical force) over the unprocessed device, as can be seen in TABLE 1.

  TABLE 1
  Maximum bending stress and maximum critical force
  for silicon penetration device with an “average” 94
  micrometer thick penetration device or probe

  		Maximum
  		Bending	Maximum
  		Force,bend	Critical
  		(MegaPascal,	Force
  	Condition	MPa)	(Newton, N)

  	Polished silicon wafer	1227	0.251
  	reference
  	Unprocessed penetration	455	0.093
  	device (roughened
  	surface from KOH
  	micromachining etch)
  	Penetration device with ˜1	665	0.136
  	micrometer thermal
  	silicon oxide surface
  	coating (1100° C.)
  	Penetration device with	2024	0.414
  	oxide removed via BOE
  	etch

• The maximum bending stress and maximum critical force values for the penetration device with an “average” 94 micrometer thick penetration device or probe after various steps of the present invention are provided in TABLE 1. These values provide a measure of the fracture toughness of the penetration device, with higher values indicating increased toughness. Standard MEMS fabrication techniques to produce silicon penetration devices include micromachining the silicon wafer with wet etchants such as potassium hydroxide solution. Prior to such treatment, a silicon penetration device with the initial reference surface of the polished silicon wafer has a maximum bending stress of 1227 Mpa and a maximum critical force of 0.251 N. After standard micromachining with a potassium hydroxide solution etch, the maximum bending stress decreases to 455 Mpa and the maximum critical force decreases to 0.093 N. This etching process increases surface roughness, producing a corresponding increase in surface defects where microcracks can initiate and thus decrease the fracture toughness of the penetration device.[0026]
• The two-step method of the present invention has several advantages over the prior art. For instance, in the first step, when thermally growing[0027]silicon oxide layer12bfrom the surface ofsilicon substrate10a,silicon oxide layer12bactually becomes the outer surface of the needle or probe. This outer surface is smoother than the original roughened surface ofsubstrate10a,with the interface betweensilicon oxide layer12bandsubstrate10bpossibly also becoming more smooth during the oxide formation process. Whensilicon oxide layer12bis then removed, the resultant penetration device exhibits a significant increase in fracture toughness in comparison to the unprocessed device.
• The two processing steps of the present invention will now be described. In step one,[0028]silicon oxide layer12bis grown at elevated temperatures on the surface ofsilicon substrate10a.Thesilicon substrate10aitself serves as the source of silicon in the reaction to formsilicon oxide layer12b,the outer surface ofsubstrate10b.Silicon has a significantly greater coefficient of thermal expansion than does silicon oxide. Thus, whensilicon oxide layer12bis formed at an elevated temperature and silicon microprobe device subsequently cooled to room temperature,silicon substrate10bundergoes a greater contraction than doessilicon oxide layer12b.This placessilicon oxide layer12bin a state of compression, thereby tending to hold the microflaws together and inhibiting failure. Further, photomicrographs of the oxide surface indicate that it is visibly smoother than the surface ofunprocessed substrate10a.Referring to TABLE 1, the values of the maximum bending stress and maximum critical force for a penetration device withsilicon oxide layer12bof the present invention are greater than those for unprocessed precursorsilicon penetration device10a,which had been micromachined using a wet KOH (potassium hydroxide) etch.
• In the second step of the present invention,[0029]silicon oxide layer12bis removed fromsubstrate10bthereby revealing the newly-exposed silicon surface ofsubstrate10c.Again referring to TABLE 1, the values of the maximum bending stress and maximum critical force for a device withsubstrate10c surface characteristics are a factor of 3.04 greater than those for a device comprisingsilicon substrate10bandsilicon oxide layer12band, most unexpectedly, 1.65 greater than those for the polished silicon wafer reference device. The reasons for this unexpected increase in fracture toughness are not known. Two possible postulates may contribute to the observed increase.
• a. In step 1, when[0030]silicon oxide layer12bis grown onsubstrate10aat elevated temperatures, annealing may possibly occur at the interface betweensilicon oxide layer12band the single crystal silicon substrate, creating a smoother silicon boundary. Therefore, whensilicon oxide layer12bis removed fromsubstrate10bin step 2, the newly uncovered surface ofsubstrate10cis smoother with fewer defects
• b. A layer of polycrystalline silicon may possibly recrystallize at the silicon oxide/silicon interface during the elevated temperature processing. The polycrystalline silicon layer exposed when the oxide layer is removed may contribute to a decrease in surface roughness. Further, polycrystalline silicon has a higher fracture toughness than single crystal silicon.[0031]
• In sum, a preferred embodiment of the present invention comprises the following processing steps:[0032]
• 1. The unprocessed penetration device is RCA cleaned. RCA clean is a standard semiconductor cleaning process using two solutions in sequence. The first is an aqueous solution of ammonia and hydrogen peroxide; the second an aqueous solution of hydrochloric acid and hydrogen peroxide.[0033]
• 2. The RCA-cleaned device is placed in a Tylan oxide furnace and the temperature is increased to 1100 degrees Celsius.[0034]
• 3. The penetration device is exposed to a dry oxygen environment for five (5) minutes;[0035]
• 4. A wet steam is introduced into the furnace for a variable predetermined time resulting in[0036]silicon oxide layer12bgrowth onsubstrate10bof approximately forty (40) Angstroms per minute;
• 5. The dry oxygen environment is reintroduced into the furnace;[0037]
• 6. The penetration device is removed from the furnace having approximately one (1) micrometer of[0038]silicon oxide layer12bgrowth on the top and bottom surfaces ofsubstrate10a;and
• 7. The penetration device is placed in a buffered oxide etchant for approximately thirty (30) minutes, removing the thermally grown oxide layer, and exposing the smoothened surface of the penetration device[0039]16 of the present invention. The buffered oxide etchant solution comprises water, ammonium fluoride, hydrofluoric acid, and ammonium hydrogen fluoride.
• The present invention further includes strengthening the penetration device by depositing a 0.5 micrometer to 1.0 micrometer thick[0040]nickel film layer14donto both sides ofsubstrate10a.Preferably, thenickel film layer14dis deposited onsubstrate10athrough a sputtering technique. The presence of thenickel film layer14donsubstrate10dreduces the effects of the strength limiting flaws on the surface of thesilicon penetration device10dby sealing and covering the defects thereon, thus inhibiting microcrack propagation and increasing fracture toughness.
• The methods of the present invention with the[0041]nickel film layer14dcomprise the following steps:
• 1. The penetration device is cleaned by submersing them into methylene chloride (CH[0042]₂Cl₂) for approximately ten (10) minutes; and
• 2. A[0043]nickel film layer14dhaving a thickness of one (1) micrometer is sputtered onto both sides ofsubstrate10dat a power of approximately five-hundred (500) watts and at a rate of approximately four hundred and ninety-five (495) Angstroms per minute.
• The resultant silicon penetration device with[0044]nickel film layer14dexhibits significantly greater fracture toughness than the device with KOH etchedsubstrate10a.The value of the maximum bending stress for the device withnickel film layer14dis a factor of 1.19 greater than that for the device withsubstrate10aalone.
INDUSTRIAL APPLICABILITY
• It will be apparent to those skilled in the are that the objects of this invention have been achieved as described hereinbefore by providing a silicon penetration device with increased fracture toughness and method of fabrication thereof. The method comprises strengthening silicon penetration devices by thermally growing a chemically-bound silicon-containing layer on the penetration device and then subsequently stripping off the layer. The method also includes strengthening silicon penetration devices through the sputtering of thin film coatings on the silicon penetration devices. The resultant penetration devices exhibit increased fracture toughness and are capable of penetrating skin reliably and painlessly without breakage. They are useful for a wide range of blood monitoring and sampling applications.[0045]
CONCLUSION
• The foregoing description of the preferred embodiments of the subject invention have been presented for purposes of illustration and description and for a better understanding of the invention. Various changes may be made in the embodiments presented herein without departing from the concept of the invention. For example, other chemicals capable of reacting with the silicon of the[0046]unprocessed penetration device10ato form a thick adherent film can be added together, individually, or in sequence during the film formation steps. Therefore, the scope of the invention is to be determined by the terminology of the following claims and the legal equivalents thereof.

Claims (27)

We claim as our invention

1. A method of forming a silicon penetration device having increased fracture toughness, the method comprising:

cleaning the surface of the silicon penetration device;

heating the cleaned silicon penetration device;

exposing the silicon penetration device to a reactive environment at elevated temperature to form an adherent film on the surface of the penetration device, the reactive environment containing one or more of the following reactants at one time, or in a sequence: oxygen, ozone, steam, hydrogen, ammonia, nitrous oxide, nitric oxide, nitrogen;

cooling the silicon penetration device; and

etching the silicon penetration device to remove at least a part of the adherent film.

2. The method ofclaim 1 wherein, during the cleaning step, the silicon penetration device is RCA cleaned.

3. The method ofclaim 1 wherein the heating step is accomplished by a Tylan oxide furnace.

4. The method ofclaim 1 wherein during the heating step the temperature of the device is raised to 1100 degrees Celsius.

5. The method ofclaim 1 wherein the cooling step begins when the silicon penetration device has approximately one (1) micrometer of film has grown on the surface of the silicon substrate.

6. The method ofclaim 1 wherein during the etching step the silicon penetration device is placed in a 6:1 solution of water and hydrofluoric acid.

7. The method ofclaim 1 wherein during the etching step the silicon penetration device is placed in a buffered oxide etchant (BOE) for approximately thirty (30) minutes such that the thermally grown surface layer is removed and the smoothened surface of the silicon substrate is exposed.

8. A method of forming a penetration device having increased fracture toughness, the method comprising:

cleaning the surface of the silicon penetration device;

heating the cleaned silicon penetration device;

exposing the silicon penetration device to a dry oxygen environment at elevated temperature to form an adherent film on the surface of the penetration device;

introducing a wet steam into the oxygen environment;

further exposing the silicon penetration device to a dry oxygen environment;

cooling the silicon penetration device; and

etching the silicon penetration device to remove at least a part of the oxide film.

9. The method ofclaim 8 wherein the first exposure of the silicon penetration device to a dry oxygen environment is for about five (5) minutes;

10. The method ofclaim 8 wherein the wet steam is introduced into the furnace for a variable predetermined time such that silicon oxide growth rate on the silicon substrate is approximately forty (40) Angstroms per minute;

11. The method ofclaim 8 wherein the cooling step begins when approximately one (1) micrometer of silicon oxide has grown on the surface of the silicon substrate.

12. A method of forming a penetration device having increased fracture toughness, the method comprising: cleaning the silicon penetration device; and depositing a nickel film on the silicon substrate.

13. The method ofclaim 12 wherein during the cleaning step the silicon penetration device is submerged into methylene chloride (CH₂Cl₂).

14. The method ofclaim 13 wherein during the cleaning step the silicon penetration device is cleaned for approximately ten (10) minutes.

15. The method ofclaim 12 wherein during the depositing step the nickel film is sputtered on the silicon substrate to a thickness of approximately one (1) micrometer.

16. The method ofclaim 12 wherein during the depositing step the nickel film is deposited on the substrate at a power of approximately five-hundred (500) watts and at a rate of approximately four hundred and ninety-five (495) Angstroms per minute.

17. A penetration device with increased fracture toughness, comprising:

an unprocessed silicon penetration device; and

an adherent film comprising silicon reacted with one or more of the following: oxygen, ozone, steam, hydrogen, ammonia, nitrous oxide, nitric oxide, nitrogen on the silicon substrate, at least a portion of which is removed by an etchant.

18. A penetration device with increased fracture toughness, comprising:

an unprocessed silicon substrate;

a silicon oxide layer on the silicon substrate, at least a portion of which is removed by an etchant.

19. The penetration device ofclaim 18 wherein the device is RCA cleaned.

20. The penetration device ofclaim 18 wherein the silicon oxide layer is formed in a Tylan oxide furnace having a temperature of approximately 1100 degrees Celsius.

21. The penetration device ofclaim 18 wherein wet steam is introduced into a furnace.

22. The penetration device ofclaim 18 wherein the silicon oxide layer has a growth rate on the silicon substrate of approximately forty (40) Angstroms per minute;

23. The penetration device ofclaim 18 wherein the silicon oxide layer has a thickness of approximately one (1) micrometer.

24. The penetration device ofclaim 18 wherein the etchant used to remove at least a portion of the silicon oxide layer is a buffered oxide etchant.

25. A penetration device with increased fracture toughness, the device comprising;

an unprocessed silicon penetration device; and

a nickel film deposited on the silicon substrate of the penetration device.

26. The penetration device ofclaim 23 wherein the nickel film is sputtered on the silicon substrate to a thickness of approximately one (1) micrometer.

27. The penetration device ofclaim 24 wherein the nickel film is deposited on the substrate at a power of approximately five-hundred (500) watts and at a rate of approximately four hundred and ninety-five (495) Angstroms per minute.

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