# US 2014/0154399 A1 · Controlling the uniformity of pecvd deposition

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 2014/0154399 A1
- Document ID: US20140154399A1
- Status: Published application
- Kind: A1
- Application number: 14/085,749
- Filed: 2013-11-20
- Published: 2014-06-05
- Earliest claimed: 2012-11-30
- Assignees: Sio2 Medical Products, Inc.
- Applicants: Sio2 Medical Products, Inc.
- Inventors: Christopher Weikart; Becky L. Clark; Adam Stevenson; Robert S. Abrams; John Belfance
- Web page: https://patentgrep.com/patent/US20140154399A1

## CPC

- A61M 5/3129: {Syringe barrels (A61M5/3205, A61M5/50 take precedence)}
- C23C 16/045: {Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates}
- C23C 16/402: {Silicon dioxide}
- C23C 16/50: using electric discharges {(generation and control of plasma in discharge tubes for surface treatment H01J37/32, H01J37/34)}
- A61M: DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY (introducing media into or onto the bodies of animals A61D7/00; means for inserting tampons A61F13/26; devices for administering food or medicines orally A61J; containers for collecting, storing or administering blood or medical fluids A61J1/05); DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY (surgery A61B; chemical aspects of surgical articles A61L); DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR {(Electrotherapy, e.g. producing anaesthesia by the use of alternating or intermittent currents A61N1/36021)}
- C23C: COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04)

## Abstract

A method and apparatus for plasma modifying a workpiece such as a syringe barrel, cartridge barrel, vial, or blood tube is described. Plasma is provided within the lumen of the workpiece. The plasma is provided under conditions effective for plasma modification of a surface of the workpiece. A magnetic field is provided in at least a portion of the lumen. The magnetic field has an orientation and field strength effective to improve the uniformity of plasma modification of the interior surface of the generally cylindrical wall. A vessel made according to the process or using the apparatus described above. A pharmaceutical package comprising the syringe barrel or vial containing a pharmaceutical preparation, secured with a closure.

## Claims

### Claim 1

A method of plasma modifying a syringe barrel or cartridge barrel having a surface to be treated, the method comprising:
providing plasma in or near the surface under conditions effective for plasma modification of the surface of the syringe barrel or cartridge barrel; and
at least part of the time while providing plasma, providing a magnetic field in or near the plasma, the magnetic field having a position, orientation, and field strength effective to improve the uniformity, density, or both of plasma modification of the surface of the syringe barrel or cartridge barrel, in which the uniformity of plasma modification is expressed as a ratio of:
one standard deviation of coating thickness/mean coating thickness and the ratio is from 0.5 to 0.2.

### Claim 2 (depends on 1)

The method of claim 1, in which the surface is a generally cylindrical interior surface defining at least a portion of a lumen.

### Claim at position 3

3-5. (canceled)

### Claim 6 (depends on 1)

The method of claim 1, in which the magnetic field is provided by providing at least one magnetic field generator near the surface, each magnetic field generator having a north pole and a south pole defining a polar axis, in which at least part of the time while providing the magnetic field, at least one magnetic field generator has its polar axis generally parallel to the axis of the surface.

### Claim 7

(canceled)

### Claim 8 (depends on 6)

The method of claim 6, in which at least part of the time while providing the magnetic field, at least two magnetic field generators, are circumferentially distributed around the surface.

### Claim at position 7

8a-8b, 9. (canceled)

### Claim 10 (depends on 6)

The method of claim 6, in which at least two of the magnetic field generators are rotated about the surface, or the surface rotates with respect to the magnetic field generators, or both, during at least a portion of the plasma treatment.

### Claim 11 (depends on 6)

The method of claim 6, in which at least one magnetic field generator is a permanent magnet.

### Claim at position 10

12-14. (canceled)

### Claim 15 (depends on 6)

The method of claim 6, further comprising at least part of the time while providing the magnetic field, translating at least one of the magnetic field generators axially along the surface, or translating the surface with respect to the magnetic field generator, or both, at a rate effective to improve the uniformity of barrel heating along the axis of the surface.

### Claim at position 12

16-37. (canceled)

### Claim 38 (depends on 1)

The method of claim 1, in which the barrel is a syringe body and needle assembly, the assembly having a needle end, a back end, and a body portion between the ends.

### Claim at position 14

39-55. (canceled)

### Claim 56 (depends on 1)

The method of claim 1, in which at least part of the time while providing the magnetic field, at least a portion of the magnetic field in at least a portion of the lumen is oriented with its polar axis extending generally in radial planes with respect to the surface.

### Claim at position 16

57-62. (canceled)

### Claim 63 (depends on 6)

The method of claim 6, in which at least part of the time while providing the magnetic field, an even number of at least four magnetic field generators are arranged about the axis to provide a quadrupole or analogous structure between axially spaced ends.

### Claim at position 18

64-71. (canceled)

### Claim 72 (depends on 1)

The method of claim 1, further comprising generating the plasma by providing an outer electrode outside the barrel and an inner electrode at least partially inside the lumen of the barrel and energizing the electrodes using radio-frequency energy.

### Claim at position 20

73-79. (canceled)

### Claim 80 (depends on 1)

The method of claim 1, in which the plasma modification of the surface comprises plasma enhanced chemical vapor deposition (PECVD).

### Claim 81 (depends on 80)

The method of claim 80, in which the inner electrode comprises a material supply tube having a generally cylindrical wall disposed within the lumen for providing gaseous material to the lumen.

### Claim 82

(canceled)

### Claim 83 (depends on 81)

The method of claim 81, in which the material supply tube generally cylindrical wall has perforations distributed axially and circumferentially along the generally cylindrical surface to pass gaseous material to the lumen.

### Claim at position 25

84-90. (canceled)

### Claim 91 (depends on 1)

The method of claim 1, in which the plasma modification is carried out at least in part at a subatmospheric pressure, in which the subatmospheric pressure is generated by at least partially evacuating a lumen at or near the surface, while the exterior of the barrel is exposed to atmospheric pressure during at least a portion of the plasma modification.

### Claim at position 27

92-93. (canceled)

### Claim 94 (depends on 1)

The method of claim 1, in which the material supplied to the lumen during at least a portion of the plasma modification comprises:
an organosiloxane precursor;
optionally an oxidizing gas; and
optionally a diluent gas.

### Claim at position 29

95-96. (canceled)

### Claim 97 (depends on 94)

The method of claim 94, in which the precursor comprises hexamethylenedisiloxane (HMDSO), octamethylcyclotetrasiloxane (OMCTS), or a combination of these.

### Claim at position 31

98-102. (canceled)

### Claim 103 (depends on 1)

The method of claim 1, in which the plasma modification comprises application of a barrier coating to the surface of the barrel.

### Claim 104 (depends on 103)

The method of claim 103, in which the barrier coating consists essentially of SiOx, in which x is from 1.5 to 2.9.

### Claim 105 (depends on 103)

The method of claim 103, in which the plasma modification comprises application of a pH protective coating to the surface of the barrel, in which the pH protective coating consists essentially of SiOxCy, in which x is from about 0.5 to about 2.4 and y is from about 0.6 to about 3.

### Claim at position 35

106-109. (canceled)

### Claim 110 (depends on 1)

The method of claim 1, in which the plasma modification is application of a coating having a mean thickness from 190 to 10 nm.

### Claim at position 37

111-180. (canceled)

### Claim 181 (depends on 1)

The method of claim 1, further comprising measuring plasma characteristics using at least one of:
a camera configured to show whether the plasma comprises streamers of non-uniform plasma versus complete fill with uniform plasma,
an optical emissions spectrometer to determine the uniformity of the plasma spectrum;
a Rogowski Coil disposed about the inner electrode or its power supply conductor to determine the uniformity of the current supplied to the plasma; or
a Langmuir probe to measure the electron temperature of the plasma.

### Claim at position 39

182-204. (canceled)

### Claim 205 (depends on 81)

The method of claim 81, in which the plasma process conditions are controlled such that the distance between the inlet tube and the wall of the syringe barrel or other part undergoing PECVD is at least 2 times as great as the Debye Length.

### Claim 206 (depends on 1)

The method of claim 1, in which the aspect ratio between the inside diameter and length of the vessel being plasma treated is at least 3:1.